Water-and oil-repellency imparting ester oligomers comprising perfluoroalkyl moieties

ABSTRACT

Fluorochemical ester compositions comprising one or more compounds or oligomers having at least on fluorine-containing repeatable unit and at least one fluorine-containing terminal group are described. The compositions are useful as coatings or incorporated as melt additives. The fluorochemical compositions impart oil and water repellency to the substrate. In other aspects, this invention relates to processes for imparting oil and water repellency characteristics to substrates and articles.

FIELD OF THE INVENTION

[0001] This invention relates to fluorochemical compositions comprisingone or more compounds or oligomers having at least onefluorine-containing repeatable unit and at least one fluorine-containingterminal group. This invention also relates to articles comprising asubstrate and the fluorochemical composition, which may be applied ascoatings or incorporated as melt additives the fluorochemicalcompositions impart oil and water repellency to the substrate. In otheraspects, this invention relates to processes for imparting oil and waterrepellency characteristics to substrates and articles.

BACKGROUND OF THE INVENTION

[0002] The use of certain fluorochemical compositions on fibers andfibrous substrates, such as textiles, paper, and leather, to impart oil-and water-repellency and soil- and stain-resistance is well known in theart. See, for example, Banks, Ed., Organofluorine Chemicals and TheirIndustrial Applications, Ellis Horwood Ltd., Chichester, England, 1979,pp. 226-234. Such fluorochemical compositions include, for example,fluorochemical guanidines (U.S. Pat. No. 4,540,497, Chang et al.),compositions of cationic and non-cationic fluorochemicals (U.S. Pat. No.4,566,981, Howells), compositions containing fluorochemical carboxylicacid and epoxidic cationic resin (U.S. Pat. No. 4,426,466, Schwartz),fluoroaliphatic carbodiimides (U.S. Pat. No. 4,215,205, Landucci),fluoroaliphatic alcohols (U.S. Pat. No. 4,468,527, Patel),fluorine-containing addition polymers, copolymers, and macromers (U.S.Pat. Nos. 2,803,615; 3,068,187; 3,102,103; 3,341,497; 3,574,791;3,916,053; 4,529,658; 5,216,097; 5,276,175; 5,725,789; 6,037,429),fluorine-containing phosphate esters (U.S. Pat. Nos. 3,094,547;5,414,102; 5,424,474), fluorine-containing urethanes (U.S. Pat. Nos.3,987,182; 3,987,227; 4,504,401; 4,958,039), fluorochemical allophanates(U.S. Pat. No. 4,606,737) fluorochemical biurets (U.S. Pat. No.4,668,406), fluorochemical oxazolidinones (U.S. Pat. No. 5,025,052), andfluorochemical piperazines (U.S. Pat. No. 5,451,622).

[0003] It has long since been well documented that the fluorochemicalsegment, F(CF₂)_(n)—, of essentially any oil- and water-repellencyimparting compound, oligomer, or polymer must have six or more carbonatoms; that is n must be equal to or greater than 6 (Philips, R. W. andDettre, R. H., J. Col. and Interface Sci., 56 (2), (1976)). However, theuse of such prior art fluorochemical compositions having fluorochemicalsegments with n >6, has been cited as a potential concern. Manypreviously known oil- and water-repellency imparting compounds oroligomers contain perfluorooctyl moieties. These surfactants ultimatelydegrade to perfluorooctyl-containing compounds. It has been reportedthat certain perfluorooctyl-containing compounds may tend tobio-accumulate in living organisms; this tendency has been cited as apotential concern regarding some fluorochemical compounds. For example,see U.S. Pat. No. 5,688,884 (Baker et al.). As a result, there is adesire for fluorine-containing compositions which are effective inproviding desired oil and water repellency, and/or stain-release orstain resistance properties, and which eliminate more effectively fromthe body (including the tendency of the composition and its degradationproducts).

SUMMARY OF THE INVENTION

[0004] In one aspect, this invention relates to chemical compositionscomprising one or more compounds or oligomers having at least onefluorine-containing repeatable unit and at least one fluorine-containingterminal group. These compounds or oligomers comprise the condensationreaction product of (a) one or more polyols; (b) one or more polyacylcompounds (such as carboxylic acids, esters, acyl halides); and (c) oneor more monofunctional fluorine-containing compounds comprising afunctional group that is reactive with the hydroxyl group of the polyol(a) or with the acyl group of the polyacyl compound (b); wherein atleast a portion of the polyol compounds further comprise at least onefluorine-containing group selected from the group consisting ofperfluoroalkyl, perfluoroheteroalkyl, and perfluoroheteroalkylene.Optionally, the fluorochemical oligomers further comprisewater-solubilizing groups and/or polymerizable groups.

[0005] As used herein, the term “oligomer” means a polymer moleculeconsisting of only a few, i.e. up to an average of 10, but preferably upto an average of 5, repeating (polymerized) or repeatable units. Eachrepeating unit comprises an ester group that is derived or derivablefrom the reaction of at least one polyol having an average of greaterthan one, preferably two or more hydroxyl moieties; and at least onepolyacyl compound having an average of greater than one, preferably twoor more acyl moieties, wherein at least a portion of the polyolcompounds further comprises at least one fluorine-containing moiety,selected from the group consisting of perfluoroalkyl, perfluoroalkylene,perfluoroheteroalkyl, and perfluoroheteroalkylene. The oligomer isterminated with one or more perfluoroalkyl groups, one or moreperfluoroheteroalkyl groups, or mixtures thereof.

[0006] Certain preferred embodiments of the fluorochemical compositionsof the present invention include those compositions comprising terminaland pendant R_(f) groups having from 1 to 12 carbons, preferably 6 orfewer carbons, and more preferably three to five carbons. Even withR_(f) groups that are relatively short (i.e. a carbon chain length ofless than eight carbon atoms), these fluorochemical compositions,surprisingly, impart excellent oil and water repellency and stainrelease or stain resistance and exhibit high dynamic water andhexadecane contact angles. Although compositions comprising low fluorinecontent are less expensive, R_(f) groups shorter than eight carbonstypically have been overlooked by those of skill in the art because theyhave been believed to impart inferior oil and water repellency and stainresistance.

[0007] When the compounds further comprise water-solubilizing groups,the fluorochemical compositions of the present invention exhibit watersolubility or water dispersability, while at the same time providingsurprisingly good water-repellency and stain-release properties. Theseembodiments include, for example, those chemical compositions comprisinga ester oligomer containing one or more solubilizing groups. Thesolubilizing groups include carboxylate, sulfate, sulfonate, phosphate,phosphonate, ammonium, quaternary ammonium, and the like, and mixturesthereof. These embodiments are particularly well suited for uniformtopical treatments on a variety of substrates where the use of organicsolvents is undesirable.

[0008] When the compounds further comprise polymerizable groups, thecoatings derived from the fluorochemical compositions of the presentinvention exhibit increased durability. That is the repellency andstain-resistant properties remain even after abrasion, scrubbing,washing, exposure to wear, and the like.

[0009] Another embodiment of the present invention relates to a coatingcomposition comprising a solution comprising the fluorochemicalcomposition of the present invention and a solvent. In this embodiment,the fluorochemical composition is dissolved or dispersed in the solvent.When applied to a substrate, this coating composition provides a uniformdistribution of the chemical composition on the substrate withoutaltering the appearance of the substrate. This invention further relatesto a method for imparting water- and oil-repellency, stain-release, orstain-resistance characteristics to a substrate, comprised of one ormore surfaces, comprising the steps of:

[0010] (a) applying the coating composition of the present inventiononto one or more surfaces of the substrate wherein the coatingcomposition comprises:

[0011] (i) at least one solvent; and

[0012] (ii) the fluorochemical composition of the invention; and

[0013] (b) curing the coating composition.

[0014] The fluorochemical compositions of the present invention can beapplied as coatings to a wide variety of substrates, for example, bytopical application, to impart oil- and water-repellency, stain-release,and stain-resistant properties to the substrates. In testing substratescoated with the fluorochemical compositions of the present invention,unexpectedly high dynamic water and hexadecane contact angles have beenobserved.

[0015] When applied as a coating, the chemical compositions of thepresent invention can provide a uniform film. Applied as a coating, thechemical compositions of the present invention do not change theappearance of the substrate to which they are applied. In addition, withcertain chemical compositions of the present invention, there is no needfor high temperature curing; they can be cured (i.e., dried) at ambienttemperature. Some compositions require higher temperature, i.e. up toabout 130° C.

[0016] The fluorochemical compositions of the present invention may alsobe incorporated into a polymer as a polymer melt blend. The polymercomposition comprises one or more thermoplastic or thermoset polymersand the fluorochemical composition of the invention. The presentinvention also relates to a process for preparing a repellentcomposition comprising the steps of

[0017] (a) combining the fluorochemical composition and at least onethermoplastic polymer; and

[0018] (b) melt processing the resulting combination.

[0019] The present invention further relates to a process for preparinga repellent composition comprising the steps of

[0020] (a) combining the fluorochemical composition and at least onethermosetting polymer or ceramer or the reactive precursors of saidpolymer or ceramer; and

[0021] (b) curing the resulting combination.

[0022] This invention also provides an article comprising a substratecoated or blended with the fluorochemical composition of the invention.After application and curing of the fluorochemical composition on thesubstrate or melt blending the fluorochemical composition with thesubstrate, the substrate displays surprisingly high water and hexadecanecontact angles which are normally correlated to water- andoil-repellency, stain-release, or stain-resistance properties.

[0023] Still further, this invention relates to a method for impartingwater- and oil-repellency, stain-release, or stain-resistancecharacteristics to a shaped article comprising the steps of:

[0024] (a) melt blending a fluorochemical composition with one or morethermoplastic polymers and

[0025] (b) forming the melt blend into a shaped article.

[0026] The present invention also relates to a process for preparing arepellent composition comprising the steps of

[0027] (a) combining a fluorochemical composition and at least onethermoplastic polymer; and

[0028] (b) melt processing the resulting combination.

[0029] Still further, this invention relates to a method for impartingwater- and oil-repellency, stain-release, or stain-resistancecharacteristics to an article comprising the steps of:

[0030] (a) melt blending a fluorochemical composition of the presentinvention with one or more thermoplastic polymers and

[0031] (b) forming the melt blend into a shaped article;

[0032] Definitions

[0033] Unless otherwise stated, the following terms used in thespecification and claims have the meanings given below:

[0034] “Acyloxy” means a radical—OC(O)R where R is, alkyl, alkenyl, andcycloalkyl, e.g., acetoxy, 3,3,3-trifluoroacetoxy, propionyloxy, and thelike.

[0035] “Alkoxy” means a radical—OR where R is an alkyl group as definedbelow, e.g., methoxy, ethoxy, propoxy, butoxy, and the like.

[0036] “Alkyl” means a linear saturated monovalent hydrocarbon radicalhaving from one to about twelve carbon atoms or a branched saturatedmonovalent hydrocarbon radical having from three to about twelve carbonatoms, e.g., methyl, ethyl, 1-propyl, 2-propyl, pentyl, and the like.

[0037] “Alkylene” means a linear saturated divalent hydrocarbon radicalhaving from one to about twelve carbon atoms or a branched saturateddivalent hydrocarbon radical having from three to about twelve carbonatoms, e.g., methylene, ethylene, propylene, 2-methylpropylene,pentylene, hexylene, and the like.

[0038] “Aralkylene” means an alkylene radical defined above with anaromatic group attached to the alkylene radical, e.g., benzyl,pyridylmethyl, 1-naphthylethyl, and the like.

[0039] “Cured chemical composition” means that the chemical compositionis dried or solvent has evaporated from the chemical composition fromambient temperature or higher until dryness, up to approximately 24hours.

[0040] “Fibrous substrate” means materials comprised of synthetic orinorganic fibers such as wovens, knits, nonwovens, carpets, and othertextiles; and materials comprised of natural fibers such as cotton,paper, and leather.

[0041] “Fluorocarbon monoalcohol” means a compound having one hydroxylgroup and a perfluoroalkyl or a perfluoroheteralkyl group, e.g.C₄F₉SO₂N(CH₃)CH₂CH₂OH, C₄F₉CH₂CH₂OH, C₂F₅O(C₂F₄O)₃CF₂CONHC₂H₄OH,c-C₆F₁₁CH₂OH, and the like.

[0042] “Hard substrate” means any rigid material that maintains itsshape, e.g., glass, ceramic, concrete, natural stone, wood, metals,plastics, and the like.

[0043] “Heteroacyloxy” has essentially the meaning given above foracyloxy except that one or more heteroatoms (i.e. oxygen, sulfur, and/ornitrogen) may be present in the R group and the total number of carbonatoms present may be up to 50, e.g., CH₃CH₂OCH₂CH₂C(O)O—,C₄H₉OCH₂CH₂OCH₂CH₂C(O)O—, CH₃O(CH₂CH₂O)_(n)CH₂CH₂C(O)O—, and the like.

[0044] “Heteroalkoxy” has essentially the meaning given above for alkoxyexcept that one or more heteroatoms (i.e. oxygen, sulfur, and/ornitrogen) may be present in the alkyl chain and the total number ofcarbon atoms present may be up to 50, e.g. CH₃CH₂OCH₂CH₂O—,C₄H₉OCH₂CH₂OCH₂CH₂O—, CH₃O(CH₂CH₂O)_(n)H, and the like.

[0045] “Heteroalkyl” has essentially the meaning given above for alkylexcept that one or more heteroatoms (i.e. oxygen, sulfur, and/ornitrogen) may be present in the alkyl chain, these heteroatoms beingseparated from each other by at least one carbon, e.g., CH₃CH₂OCH₂CH₂—,CH₃CH₂OCH₂CH₂OCH(CH₃)CH₂—, C₄F₉CH₂CH₂SCH₂CH₂—, and the like.

[0046] “Heteroalkylene” has essentially the meaning given above foralkylene except that one or more heteroatoms (i.e. oxygen, sulfur,and/or nitrogen) may be present in the alkylene chain, these heteroatomsbeing separated from each other by at least one carbon, e.g.,—CH₂OCH₂O—, —CH₂CH₂OCH₂CH₂—, —CH₂CH₂N(CH₃)CH₂CH₂—, —CH₂CH₂SCH₂CH₂—, andthe like.

[0047] “Heteroaralkylene” means an aralkylene radical defined aboveexcept that catenated oxygen, sulfur, and/or nitrogen atoms may bepresent, e.g., phenyleneoxymethyl, phenyleneoxyethyl,benzyleneoxymethyl, and the like.

[0048] “Halo” means fluoro, chloro, bromo, or iodo, preferably fluoroand chloro.

[0049] “Perfluoroalkyl” has essentially the meaning given above for“alkyl” except that all or essentially all of the hydrogen atoms of thealkyl radical are replaced by fluorine atoms and the number of carbonatoms is from 1 to about 12, e.g. perfluoropropyl, perfluorobutyl,perfluorooctyl, and the like.

[0050] “Perfluoroalkylene” has essentially the meaning given above for“alkylene” except that all or essentially all of the hydrogen atoms ofthe alkylene radical are replaced by fluorine atoms, e.g.,perfluoropropylene, perfluorobutylene, perfluorooctylene, and the like

[0051] “Perfluoroheteroalkyl” has essentially the meaning given abovefor “heteroalkyl” except that all or essentially all of the hydrogenatoms of the heteroalkyl radical are replaced by fluorine atoms and thenumber of carbon atoms is from 3 to about 100, e.g. CF₃CF₂OCF₂CF₂—,CF₃CF₂O(CF₂CF₂O)₃CF₂CF₂—, C₃F₇O(CF(CF₃)CF₂O)_(m)CF(CF₃)CF₂— where m isfrom about 10 to about 30, and the like.

[0052] “Perfluoroheteroalkylene” has essentially the meaning given abovefor “heteroalkylene” except that all or essentially all of the hydrogenatoms of the heteroalkylene radical are replaced by fluorine atoms, andthe number of carbon atoms is from 3 to about 100, e.g., —CF₂OCF₂—,—CF₂O(CF₂O)_(n)(CF₂CF₂O)_(m)CF₂—, and the like.

[0053] “Perfluorinated group” means an organic group wherein all oressentially all of the carbon bonded hydrogen atoms are replaced withfluorine atoms, e.g. perfluoroalkyl, perfluoroheteroalkyl, and the like.

[0054] “Polyacyl compound” means a compound containing two or more acylgroups, or derivative thereof, such as carboxylic acid, ester, or acylhalide, attached to a multivalent organic group, e.g. dimethyl adipate,and the like.

[0055] “Polyol” means an organic compound or polymer with an average ofat least about 2 primary or secondary hydroxyl groups per molecule, e.g.ethylene glycol, propylene glycol, 1,6-hexanediol, and the like.

[0056] “Porous” means capable of imbibing a liquid.

DETAILED DESCRIPTION OF THE ILLUSTRATIVE EMBODIMENTS OF THE INVENTION

[0057] The fluorochemical compositions of the present invention comprisethe condensation reaction product of (a) one or more fluorinatedpolyols; (b) one or more polyacyl compounds (such as carboxylic acids,esters, acyl halides); and (c) one or more monofunctionalfluorine-containing compounds comprising a functional group that isreactive with the hydroxyl group of the polyol (a) or the acyl group ofthe polyacyl compound (b). The fluorinated polyol compounds furthercomprise at least one fluorine-containing group selected from the groupconsisting of perfluoroalkyl, perfluoroheteroalkyl, andperfluoroheteroalkylene. The ester oligomers may further comprises oneor more non-fluorinated polyols.

[0058] Optionally the compounds may further comprise one or morewater-solubilizing groups by the further reaction product of a compoundcomprising one or more water solubilizing groups selected from the groupconsisting of carboxylate, sulfate, sulfonate, phosphate, phosphonate,ammonium, and quaternary ammonium groups, and at least one electrophilicor nucleophilic moiety reactive with a hydroxyl group or an acyl group.

[0059] Optionally the compounds may further comprise one or morepolymerizable groups by the further reaction product of a compoundcomprising one or more polymerizable groups and at least oneelectrophilic or nucleophilic moiety reactive with a hydroxyl group oran acyl group.

[0060] The compound or oligomer comprises at least one repeatable orrepeating polymerized unit. Each repeatable or repeating unit comprisesone or more pendant or in-chain fluorine-containing groups selected fromthe group consisting of perfluoroalkyl, perfluoroalkylene,perfluoroheteroalkyl, and perfluoroheteroalkylene, and an ester groupthat is formed from the reaction between a polyol and a polyacylcompound. The compound or oligomer is terminated with (i) one or moreperfluoroalkyl groups, one or more perfluoroheteroalkyl groups, or amixture thereof. For brevity “oligomer” shall be inclusive of compoundsand oligomers.

[0061] In one preferred embodiment, the fluorochemical composition ofthe present invention comprises a mixture of ester molecules arisingfrom the reaction of (a) one or more polyacyl compounds, (b) one or morepolyols, and (c) one or more fluorochemical monofunctional compounds,wherein at least one of said polyols compounds comprises a fluorinatedgroup. The mixture of ester molecules preferably comprises estermolecules having a varying number of repeating or repeatable units,including zero, one, two, and more repeating units. This mixture ofester molecules comprising a varying number of repeating units allowssimple blending of the above components in preparing the fluorochemicalcomposition.

[0062] The fluorochemical composition of the present invention comprisesa mixture of ester molecules arising from the reaction of at least onediacyl compound (or a derivative thereof, for example, a dicarboxylicacid halide, a dicarboxylic acid anhydride, or a dicarboxylic acidester), at least one fluorinated polyol, and at least onefluorine-containing monoalcohol or fluorine-containing monocarboxylicacid (or derivative), with the proviso that at least a portion of thepolyol compounds is comprised of a pendant or in-chainfluorine-containing group.

[0063] Thus, the fluorochemical composition can comprise a singlefluorine-containing ester compound or oligomer having a certain numberof the specified repeating or repeatable units (a number greater than orequal to one), or it can comprise a mixture of such compounds and/oroligomers of varying numbers of repeat units. Preferably, thecomposition comprises a mixture of ester molecules of varying structure,more preferably, a mixture of at least one ester oligomer (2 or morerepeat units) and at least one ester compound (1 repeatable unit). Theoverall fluorochemical composition generally contains, relative to theamount of solids present in the system, at least about 3 weight percent,preferably at least about 5 weight percent, carbon-bound fluorine in theform of fluorochemical groups.

[0064] The ester compounds and oligomers may be represented by thefollowing formula (I):

R_(F)Q[OR²]_(o)[—OC(O)—R¹—C(O)O—R²O—]_(n)[C(O)—R¹—C(O)]_(m)—Z  (I)

[0065] wherein:

[0066] o is a number from 0 to 1 inclusive;

[0067] n is a number from 1 to 10 inclusive;

[0068] m is is number from 0 to 1 inclusive;

[0069] R_(f) is a perfluoroalkyl group having 1 to 12, preferably 6 orfewer, most preferably 3 to 5 carbon atoms, or a perfluoroheteroalkylgroup having 3 to about 50 carbon atoms with all perfluorocarbon chainspresent having 1 to 6, preferably 1 to 4 carbon atoms;

[0070] Q is a divalent linking group;

[0071] R¹ is a polyvalent organic groups that is a residue of a polyacylcompound, that is a straight or branched chain alkylene, cycloalkylene,or heteroalkylene group of 1 to 14 carbon atoms, preferably 1 to 8carbon atoms, more preferably 1 to 4 carbon atoms, and most preferablytwo carbon atoms; or an arylene of 6 to 12 carbon atoms;

[0072] R² is a divalent organic group that is a residue of the polyol,at least a portion of which are substituted with or contain one or moreperfluoroalkyl groups, perfluoroheteroalkyl groups,perfluoroheteroalkylene groups, or mixtures thereof; and

[0073] Z is R_(f)Q—, a water-solubilizing group, or a polymerizablegroup.

[0074] With respect to the above-described R_(f) groups, it is preferredthat the R_(f) group have 6 or fewer carbon atoms. It is believed thatthe shorter-chain R_(f) groups have a reduced tendency to bioaccumulateas described in U.S. Pat. No. 5,688,884.

[0075] With respect to the above-described R¹ groups, it will beunderstood that the R¹ group may further be substituted with a pendantacyl group (or equivalent thereof), as would be the case if the polyacylcompound were a triacyl compound such as a triester. The “third” acylgroup, pendant from R¹, may serve as a point of attachment of apolymerizable compound, or a water-solubilizing compound. Similarly, theR² groups may be further substituted with pendent hydroxy groups, aswould be the case if the polyol were a triol. The “third” hydroxy group,pendant from R², may also serve as a point of attachment of apolymerizable compound, or a water-solubilizing compound.

[0076] Suitable linking groups Q include the following structures inaddition to a covalent bond. For the purposes of this list, each k isindependently an integer from 0 to about 20, R₁′ is hydrogen, phenyl, oralkyl of 1 to about 4 carbon atoms, and R₂′ is alkyl of 1 to about 20carbon atoms. Each structure is non-directional, i.e. —(CH₂)_(k)C(O)O—isequivalent to —O(O)C(CH₂)_(k)—. —SO₂NR₁′(CH₂)_(k)O(O)C——CONR₁′(CH₂)_(k)O(O)C— —(CH₂)_(k)O(O)C— —CH₂CH(OR₂′)CH₂O(O)C——(CH₂)_(k)C(O)O— —(CH₂)_(k)SC(O)— —(CH₂)_(k)O(CH₂)_(k)O(O)C——(CH₂)_(k)S(CH₂)_(k)O(O)C— —(CH₂)_(k)SO₂(CH₂)_(k)O(O)C——(CH₂)_(k)S(CH₂)_(k)OC(O)— —(CH₂)_(k)SO₂NR₁′(CH₂)_(k)O(O)C——(CH₂)_(k)SO₂— —SO₂NR₁′(CH₂)_(k)O— —SO₂NR₁′(CH₂)_(k)——(CH₂)_(k)O(CH₂)_(k)C(O)O— —(CH₂)_(k)SO₂NR₁′(CH₂)_(k)C(O)O——(CH₂)_(k)SO₂(CH₂)_(k)C(O)O— —CONR₁′(CH₂)_(k)C(O)O——(CH₂)_(k)S(CH₂)_(k)C(O)O— —CH₂CH(OR₂′)CH₂C(O)O— —SO₂NR₁′(CH₂)_(k)C(O)O——(CH₂)_(k)O— —OC(O)NR′(CH₂)_(k)— —(CH₂)_(k)NR₁′— —C_(k)H_(2k)—OC(O)NH——C_(k)H_(2k)—NR₁′C(O)NH—, and —(CH₂)_(k)NR₁′C(O)O—

[0077] It will be understood that mixtures of compounds corresponding tothe general formula may be represented, in addition to single compounds,and that 0, m and n may be represented by non-integral values.

[0078] Preferred classes of fluorine-containing ester compounds andoligomers are those represented by the following formulas

R_(f)ZR¹—O—(C═O)—R³—(C═O)—O—[R⁴—O—(C═O)—R³—(C═O)—O]_(n)—R¹ZR_(f) formula(IV)

R_(f)ZR¹—(C═O)—O—R⁴—O—(C═O)—[R³—(C═O)—O—R⁴—O—(C═O)]_(n)—R¹ZR_(f) formula(V)

[0079] (with those of Formulas IV being more preferred) wherein eachR¹ZR_(f) is independently the residue of at least onefluorine-containing monoalcohol or fluorine-containing monocarboxylicacid (or derivative); each R³ and each R⁴ independently comprises atleast one aliphatic, heteroaliphatic, saturated alicyclic, saturatedheteroalicyclic, aromatic, heteroaromatic, or polymeric moiety; and n isan integer of at least one; with the proviso that R⁴ comprises a pendantor in-chain fluorine-containing group. The aromatic or heteroaromaticmoiety can comprise one or more rings (which can be fused or can beseparated by one or more spacer groups, for example, an aliphaticgroup), and the adjacent ester groups can be bonded to a single ring orto separate rings of the aromatic or heteroaromatic moiety. The ringscan be substituted with other groups that do not interfere with thereactivity of carboxylic acid or hydroxyl groups, do not causeundesirable side reactions, and do not cause decomposition of theresulting fluorochemical composition during use (for example, one ormore halogen, alkyl, alkoxy, or aryl groups substituted for one or morering-bonded hydrogen atoms). The polymeric moiety preferably has anumber average molecular weight in the range of about 500 to about 4000(more preferably, about 1000 to about 2500).

[0080] R_(f), Z, and R¹ are as described. When a fluorine-containingmonocarboxylic acid (or derivative) is used, Z and R¹ taken together canbe a covalent bond. When R³ is aromatic, R³ is preferably phenylene,napthalene, biphenylene, bis(phenylene)methylene, orbis(phenylene)propylidene (more preferably, phenylene; most preferably,meta- or para-phenylene). When R⁴ is not comprised of afluorine-containing group it is preferably a divalent aliphatic,saturated alicyclic, aliphatic polyester, or poly(oxyalkylene) moiety;more preferably, a divalent aliphatic, aliphatic polyester, orpoly(oxyalkylene) moiety; even more preferably, hexylene, ethylene,propylene, butylene, neopentylene, ethyleneoxyethylene,bis(ethyleneoxycarbonyl)phenylene, polycaprolactone, polyoxyethylene, orpolyoxypropylene; most preferably, hexylene, butylene, ethylene, orpropylene. n is generally an integer in the range of 1 to about 10;preferably, 1 to 8; more preferably, 1 to 6; most preferably, 1 to 4.

[0081] Polyols, suitable for use in preparing the fluorochemicalcompositions of the present invention comprising a mixture of polyolmolecules, include those organic polyols that have an average hydroxylfunctionality of greater than 1 (preferably about 2 to 3; mostpreferably, about 2, as diols are most preferred). The hydroxyl groupscan be primary or secondary, with primary hydroxyl groups beingpreferred for their greater reactivity.

[0082] Suitable polyols include those that comprise at least onealiphatic, heteroaliphatic, alicyclic, heteroalicyclic, aromatic,heteroaromatic, or polymeric moiety. Preferred polyols are aliphatic orpolymeric polyols that contain hydroxyl groups as terminal groups.

[0083] The polyols may comprise at least one fluorine-containing groupselected from the group consisting of perfluoroalkyl,perfluoroheteroalkyl, and perfluoroalkylene moieties. All of theperfluorocarbon chains, comprising these perfluoro moieties, arepreferably six or fewer carbon atoms. Perfluoroalkyl moieties arepreferred, with perfluoroalkyl moieties having 6 or fewer carbon atomsbeing preferred and 3 to 5 carbon atoms being most preferred.Perfluoroheteroalkyl moieties may have 3 to 50 carbon atoms.Perfluoroheteroalkylene groups may have from about 3 to about 50 carbonatoms. Perfluoroheteroalkyl and alkylene moieties are preferablyperfluoropolyethers with no perfluorocarbon chain of more than sixcarbon atoms.

[0084] Mixtures of fluorinated and non-fluorinated polyols may beadvantageously utilized in preparing certain of the fluorochemicalcompositions of the instant invention. For example, inclusion of anon-fluorinated polyol can alter the melt temperature of thefluorochemical composition, making it more effective at the processingtemperatures normally used in a given application. Increased costeffectiveness is also achieved by replacing a portion of the moreexpensive fluorinated polyol(s) with the less expensive non-fluorinatedpolyol(s). The selection of the non-fluorinated polyol(s) and the amountto use is determined by the performance requirements, for example melttemperature and repellency. A useful range of ratios of non-fluorinatedpolyol(s) to fluorinated polyols is about 1:1 to about 1:100.

[0085] Thus, the fluorochemical ester oligomer may comprise thecondensation reaction products of one or more fluorinated polyols, oneor more non-fluorinated polyols, one or more polyacyl compounds and oneor more monofunctional fluorine-containing compounds.

[0086] Polyols useful in the present invention may optionally besubstituted with or contain other groups, including water-solubilizinggroups and polymerizable groups. Solubilizing groups includecarboxylate, sulfate, sulfonate, phosphate, phosphonate, ammonium,quaternary ammonium, and the like. Polymerizable groups includeacrylate, methacrylate, vinyl, allyl, glycidyl, and the like. Both thefluorinated and non-fluorinated polyols may further comprise awater-solubilizing or polymerizable groups.

[0087] Representative examples of suitable fluorinated polyols comprisedof at least one fluorine-containing group include R_(f)SO₂N(CH₂CH₂OH)₂such as N-bis(2-hydroxyethyl)perfluorobutylsulfonamide;R_(f)OC₆H₄SO₂N(CH₂CH₂OH)₂; R_(f)SO₂N(R′)CH₂CH(OH)CH₂OH such asC₆F₁₃SO₂N(C₃H₇)CH₂CH(OH)CH₂OH; R_(f)CH₂CON(CH₂CH₂OH)₂;R_(f)CON(CH₂CH₂OH)₂; CF₃CF₂(OCF₂CF₂)₃OCF₂CON(CH₃)CH₂CH(OH)CH₂OH;R_(f)OCH₂CH(OH)CH₂OH such as C₄F₉OCH₂CH(OH)CH₂OH;R_(f)CH₂CH₂SC₃H₆OCH₂CH(OH)CH₂OH; R_(f)CH₂CH₂SC₃H₆CH(CH₂OH)₂;R_(f)CH₂CH₂SCH₂CH(OH)CH₂OH; R_(f)CH₂CH₂SCH(CH₂OH)CH₂CH₂OH;R_(f)CH₂CH₂CH₂SCH₂CH(OH)CH₂OH such as C₅F₁₁(CH₂)₃SCH₂CH(OH)CH₂OH;R_(f)CH₂CH₂CH₂OCH₂CH(OH)CH₂OH such C₅F₁₁(CH₂)₃OCH₂CH(OH)CH₂OH;R_(f)CH₂CH₂CH₂OC₂H₄OCH₂CH(OH)CH₂OH; R_(f)CH₂CH₂(CH₃)OCH₂CH(OH)CH₂OH;R_(f)(CH₂)₄SC₃H₆CH(CH₂OH)CH₂OH; R_(f)(CH₂)₄SCH₂CH(CH₂OH)₂;R_(f)(CH₂)₄SC₃H₆OCH₂CH(OH)CH₂OH; R_(f)CH₂CH(C₄H₉)SCH₂CH(OH)CH₂OH;R_(f)CH₂OCH₂CH(OH)CH₂OH; R_(f)CH2CH(OH)CH₂SCH₂CH₂OH;R_(f)CH₂CH(OH)CH₂SCH₂CH₂OH; R_(f)CH₂CH(OH)CH₂OCH₂CH₂OH;R_(f)CH₂CH(OH)CH₂OH; R_(f)R″SCH(R″′OH)CH(R″′OH)SR″R_(f);(R_(f)CH₂CH₂SCH₂CH₂SCH₂)₂C(CH₂OH)₂;((CF₃)₂CFO(CF₂)₂(CH₂)₂SCH₂)₂C(CH₂OH)₂; (R_(f)R″SCH₂)₂C(CH₂OH)₂;1,4-bis(1-hydroxy-1,1-dihydroperfluoroethoxyethoxy)perfluoro-n-butane(HOCH₂CF₂OC₂F₄O(CF₂)₄OC₂F₄OCF₂CH₂OH);1,4-bis(1-hydroxy-1,1-dihydroperfluoropropoxy)perfluoro-n-butane(HOCH₂CF₂CF₂O(CF₂)₄OCF₂CF₂CH₂OH); fluorinated oxetane polyols made bythe ring-opening polymerization of fluorinated oxetane such asPoly-3-Fox™ (available from Omnova Solutions, Inc., Akron Ohio);polyetheralcohols prepared by ring opening addition polymerization of afluorinated organic group substituted epoxide with a compound containingat least two hydroxyl groups as described in U.S. Pat. No.4,508,916(Newell et al); and perfluoropolyether diols such as Fomblin™ ZDOL(HOCH₂CF₂O(CF₂O)₈₋₁₂(CF₂CF₂O)₈₋₁₂CF₂CH₂OH, available from Ausimont);wherein R_(f) is a perfluoroalkyl group having 1 to 6 carbon atoms, or aperfluoroheteroalkyl group having 3 to about 50 carbon atoms with allperfluorocarbon chains present having 6 or fewer carbon atoms, ormixtures thereof; R′ is alkyl of 1 to 4 carbon atoms; R″ is branched orstraight cahin alkylene of 1 to 12 carbon atoms, alkylenethio-alkyleneof 2 to 12 carbon atoms, alkylene-oxyalkylene of 2 to 12 carbon atoms,or alkylene iminoalkylene of 2 to 12 carbon atoms, where the nitrogenatom contains as a third substituent hydrogen or alkyl of 1 to 6 carbonatoms; and R′″ is a straight or branched chain alkylene of 1 to 12carbon atoms or an alkylene-polyoxyalkylene of formulaC_(r)H₂r(OC_(S)H_(2S))n where r is 1-12, s is 2-6, and t is 1-40.

[0088] Preferred polyols comprised of at least one fluorine-containinggroup include N-bis(2-hydroxyethyl)perfluorobutylsulfonamide;fluorinated oxetane polyols made by the ring-opening polymerization offluorinated oxetane such as Poly-3-Fox™ (available from OmnovaSolutions, Inc., Akron Ohio); polyetheralcohols prepared by ring openingaddition polymerization of a fluorinated organic group substitutedepoxide with a compound containing at least two hydroxyl groups asdescribed in U.S. Pat. No. 4,508,916 (Newell et al); perfluoropolyetherdiols such as Fomblin™ ZDOL (HOCH₂CF₂O(CF₂O)₈₋₁₂(CF₂CF₂O)₈₋₁₂CF₂CH₂OH,available from Ausimont); 1,4-bis(1-hydroxy-1,1-dihydroperfluoroethoxyethoxy)perfluoro-n-butane(HOCH₂CF₂OC₂F₄O(CF₂)₄OC₂F₄OCF₂CH₂OH); and1,4-bis(1-hydroxy-1,1-dihydroperfluoropropoxy)perfluoro-n-butane(HOCH₂CF₂CF₂O(CF₂)₄OCF₂CF₂CH₂OH).

[0089] More preferred polyols comprised of at least onefluorine-containing group includeN-bis(2-hydroxyethyl)perfluorobutylsulfonamide;1,4-bis(1-hydroxy-1,1-dihydroperfluoropropoxy)perfluoro-n-butane(HOCH₂CF₂CF₂O(CF₂)₄OCF₂CF₂CH₂OH).

[0090] Representative examples of suitable non-polymeric,non-fluorinated polyols include alkylene glycols, polyhydroxyalkanes,and other polyhydroxy compounds. The alkylene glycols include, forexample, 1,2-ethanediol; 1,2-propanediol; 3-chloro-1,2-propanediol;1,3-propanediol; 1,3-butanediol; 1,4-butanediol;2-methyl-1,3-propanediol; 2,2-dimethyl-1,3-propanediol(neopentylglycol); 2-ethyl-1,3-propanediol; 2,2-diethyl-1,3-propanediol;1,5-pentanediol; 2-ethyl-1,3-pentanediol;2,2,4-trimethyl-1,3-pentanediol; 3-methyl-1,5-pentanediol; 1,2-, 1,5-,and 1,6-hexanediol; 2-ethyl-1,6-hexanediol;bis(hydroxymethyl)cyclohexane; 1,8-octanediol; bicyclo-octanediol;1,10-decanediol; tricyclo-decanediol; norbornanediol; and1,18-dihydroxyoctadecane. The polyhydroxyalkanes include, for example,glycerine; trimethylolethane; trimethylolpropane;2-ethyl-2-(hydroxymethyl)-1,3-propanediol; 1,2,6-hexanetriol;pentaerythritol; quinitol; mannitol; and sorbitol. The other polyhydroxycompounds include, for example, polyols such as di(ethylene glycol);tri(ethylene glycol); tetra(ethylene glycol); tetramethylene glycol;dipropylene glycol; diisopropylene glycol; tripropylene glycol;bis(hydroxymethyl)propionic acid;N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane; bicine;1,11-(3,6-dioxaundecane)diol; 1,14-(3,6,9,12-tetraoxatetradecane)diol;1,8-(3,6-dioxa-2,5,8-trimethyloctane)diol;1,14-(5,10-dioxatetradecane)diol; castor oil; 2-butyne-1,4-diol;N,N-bis(hydroxyethyl)benzamide; 4,4′-bis(hydroxymethyl)diphenylsulfone;1,4-benzenedimethanol; 1,3-bis(2-hydroxyethyoxy)benzene;1,2-dihydroxybenzene; resorcinol; 1,4-dihydroxybenzene; 3,5-, 2,6-,2,5-, and 2,4-dihydroxybenzoic acid; 1,6-, 2,6-, 2,5-, and2,7-dihydroxynaphthalene; 2,2′- and 4,4′-biphenol;1,8-dihydroxybiphenyl; 2,4-dihydroxy-6-methyl-pyrimidine;4,6-dihydroxypyrimidine; 3,6-dihydroxypyridazine; bisphenol A;4,4′-ethylidenebisphenol; 4,4′-isopropylidenebis(2,6-dimethylphenol);bis(4-hydroxyphenyl)methane; 1,1-bis(4-hydroxyphenyl)-1-phenylethane(bisphenol C); 1,4-bis(2-hydroxyethyl)piperazine; bis(4-hydroxyphenyl)ether; as well as other aliphatic, heteroaliphatic, saturated alicyclic,aromatic, saturated heteroalicyclic, and heteroaromatic polyols; and thelike, and mixtures thereof.

[0091] Representative examples of useful polymeric non-fluorinatedpolyols include polyoxyethylene, polyoxypropylene, and ethyleneoxide-terminated polypropylene glycols and triols of molecular weightsfrom about 200 to about 2000, corresponding to equivalent weights ofabout 100 to about 1000 for the diols or about 70 to about 700 fortriols; polytetramethylene glycols of varying molecular weight;polydialkylsiloxane diols of varying molecular weight;hydroxy-terminated polyesters and hydroxy-terminated polylactones (e.g.,polycaprolactone polyols); hydroxy-terminated polyalkadienes (e.g.,hydroxyl-terminated polybutadienes); and the like. Mixtures of polymericpolyols can be used if desired.

[0092] Useful commercially available polymeric non-fluorinated polyolsinclude Carbowax™ poly(ethylene glycol) materials in the number averagemolecular weight (M_(n)) range of from about 200 to about 2000(available from Union Carbide Corp.); poly(propylene glycol) materialssuch as PPG-425 (available from Lyondell Chemicals); block copolymers ofpoly(ethylene glycol) and poly(propylene glycol) such as Pluronic™ L31(available from BASF Corporation); Bisphenol A ethoxylate, Bisphenol Apropyloxylate, and Bisphenol A propoxylate/ethoxylate (available fromSigma-Aldrich); polytetramethylene ether glycols such as Polymeg™ 650and 1000 (available from Quaker Oats Company) and the Terathane™ polyols(available from DuPont); hydroxyl-terminated polybutadiene resins suchas the Poly bd™ materials (available from Elf Atochem); the “PeP” series(available from Wyandotte Chemicals Corporation) of polyoxyalkylenetetrols having secondary hydroxyl groups, for example, “PeP” 450, 550,and 650; polycaprolactone polyols with M_(n) in the range of about 200to about 2000 such as Tone™ 0201, 0210, 0301, and 0310 (available fromUnion Carbide); “Paraplex™ U-148” (available from Rohm and Haas), analiphatic polyester diol; polyester polyols such as the Multron™poly(ethyleneadipate)polyols (available from Mobay Chemical Co.);polycarbonate diols such as Duracarb™ 120, a hexanediol carbonate withM_(n)=900 (available from PPG Industries Inc.); and the like; andmixtures thereof.

[0093] Preferred non-fluorinated polyols include 1,2-ethanediol; 1,2-and 1,3-propanediol; 1,3- and 1,4-butanediol; neopentylglycol;1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,2-, 1,5-, and1,6-hexanediol; bis(hydroxymethyl)cyclohexane; 1,8-octanediol;1,10-decanediol; di(ethylene glycol); tri(ethylene glycol);tetra(ethylene glycol); di(propylene glycol); di(isopropylene glycol);tri(propylene glycol); poly(ethylene glycol) diols (number averagemolecular weight of about 200 to about 1500); poly(di(ethylene glycol)phthalate) diol (having number average molecular weights of, forexample, about 350 or about 575); poly(propylene glycols) diols (numberaverage molecular weight of about 200 to about 500); block copolymers ofpoly(ethylene glycol) and poly(propylene glycol) such as Pluronic™ L31(available from BASF Corporation); polycaprolactone diols (numberaverage molecular weight of about 200 to about 600); resorcinol;hydroquinone; 1,6-, 2,5-, 2,6-, and 2,7-dihydroxynaphthalene;4,4′-biphenol; bisphenol A; bis(4-hydroxyphenyl)methane; and the like;and mixtures thereof.

[0094] More preferred non-fluorinated polyols include 1,2-ethanediol;1,2- and 1,3-propanediol; 1,4-butanediol; neopentylglycol; 1,2- and1,6-hexanediol; di(ethylene glycol); tri(ethylene glycol);poly(di(ethylene glycol) phthalate) diol (having number averagemolecular weights of, for example, about 350 or about 575);poly(ethylene glycol) diols (having number average molecular weights of,for example, about 200, 300, 400); polypropylene glycol (having a numberaverage molecular weight of, for example, about 425); dimer diol;polycaprolactone diol (having a number average molecular weight of, forexample, about 530); 3,5-dihydroxybenzene; bisphenol A; resorcinol;hydroquinone; and mixtures thereof.

[0095] Polyacyl compounds and derivatives thereof (for example,dicarboxylic acid halides, dicarboxylic acid anhydrides, anddicarboxylic acid esters) suitable for use in preparing thefluorochemical composition comprise at least one aliphatic,heteroaliphatic (that is, containing in-chain heteroatoms, such asnitrogen, oxygen, or sulfur), saturated alicyclic, saturatedheteroalicyclic, or polymeric moiety. The polyacyl compounds canoptionally contain one or more “non-interfering” groups (groups that donot interfere with the reactivity of the acyl groups, do not causeundesirable side reactions, and do not cause decomposition of theresulting fluorochemical composition), for example, alkyl, sulfonate,ester, ether, halo, haloalkyl, amide, or carbamate groups. Preferably,the polyacyl compounds are aliphatic in nature.

[0096] Acyl derivatives are sometimes preferred over acids for a varietyof reasons. For example, acyl halides provide both relatively fastreaction rates and reactions that tend to go to completion. Theresulting HCl is volatile and can be removed under vacuum or by otherremoval means, such as by water washing.

[0097] For applications in which evolution of HCl is undesirable, alower alkyl acyl ester can be used. Use of such lower alkyl esters canfacilitate processing, due to their lower melting points and greatersolubility in some solvents (relative to the corresponding acids).Continuous removal of the resulting lower alkyl alcohol can be employedto bring the reaction to completion. A catalyst, such asp-toluenesulfonic acid or trifluoromethanesulfonic acid, can also beused and can be selected so as to be removable or deactivatable (e.g.reacted with CaO) after reaction is complete, or so as to cause minimaldecomposition of the resulting fluorochemical composition under useconditions.

[0098] Anhydrides can also be used. Particularly useful anhydridederivatives of dicarboxylic acids are cyclic anhydrides, which reactrelatively rapidly with an alcohol to form an ester and a carboxylicacid group. This allows a preponderance of monoester/monocarboxylic acidto be formed from the reaction of the cyclic anhydride with one alcohol(such as the fluorine-containing monoalcohol), followed by reaction ofthe remaining carboxylic acid groups with a second alcohol (such as thepolyol). Alternatively, the remaining carboxylic acid groups can firstbe converted to the corresponding acid halide and then reacted with thesecond alcohol.

[0099] Representative examples of suitable dicarboxylic acids anddicarboxylic acid derivatives include the following acids and theircorresponding esters, halides, and anhydrides: azelaic; maleic; fumaric;itaconic; 1,5-pent-2-enedioic; adipic; 2-methyleneadipic;3-methylitaconic; 3,3-dimethylitaconic; sebacic; suberic; pimelic;succinic; benzylsuccinic; sulfosuccinic; gluratic; 2-methyleneglutaric;2-sulfoglutaric; 3-sulfoglutaric; diglycolic; dilactic;3,3′-(ethylenedioxy)dipropionic; dodecanedioic; 2-sulfododecanedioic;decanedioic; undecanedicarboxylic; hexadecanedicarboxylic; dimerizedfatty acids (such as those obtained by the dimerization of olefinicallyunsaturated monocarboxylic acids containing 16 to 20 carbon atoms, forexample, oleic acid and linoleic acid and the like); 1,2-, 1,4-, and1,6-cyclohexanedicarboxylic; norbornenedicarboxylic;bi-cyclooctanedicarboxylic; and other aliphatic, heteroaliphatic,saturated alicyclic, or saturated heteroalicyclic dicarboxylic acids;and the like; and mixtures thereof. Salts (for example, alkali metalsalts) of the above-described sulfonic acids can also be used.

[0100] Preferred dicarboxylic acids and dicarboxylic acid derivativesinclude succinic, adipic, dimer acid, azelaic acid, dodecanedioic acid,poly(ethylene glycol) diacid, citric acid, poly(acrylic acid), pimelic,suberic, and sebacic acids (and derivatives thereof), and the like, andmixtures thereof; with suberic, and adipic acids (and derivativesthereof), and mixtures thereof being more preferred.

[0101] When fluorochemical compositions of the present invention areused as topical treatments, aliphatic dicarboxylic acids (andderivatives thereof) are preferred.

[0102] Fluorochemical monofunctional compounds, useful in preparing thefluorochemical compositions of the present invention comprising amixture of ester molecules, include those that comprise at least oneR_(f) group. The R_(f) groups can contain straight chain, branchedchain, or cyclic fluorinated alkylene groups or any combination thereof.The R_(f) groups can optionally contain one or more heteroatoms (i.e.oxygen, sulfur, and/or nitrogen) in the carbon-carbon chain so as toform a carbon-heteroatom-carbon chain (i.e. a heteroalkylene group).Fully-fluorinated groups are generally preferred, but hydrogen orchlorine atoms can also be present as substituents, provided that nomore than one atom of either is present for every two carbon atoms. Itis additionally preferred that any R_(f) group contain at least about40% fluorine by weight, more preferably at least about 50% fluorine byweight. The terminal portion of the group is generallyfully-fluorinated, preferably containing at least three fluorine atoms,e.g., CF₃O—, CF₃CF₂—, CF₃CF₂CF₂—, (CF₃)₂N—, (CF₃)₂CF—, SF₅CF₂—.Perfluorinated aliphatic groups (i.e., those of the formulaC_(n)F_(2n+1)—) wherein n is 1 to 12 inclusive are the preferred R_(f)groups, with n=6 or fewer being more preferred and with n=3 to 5 beingthe most preferred. Further, it is preferred that the fluorochemicalmonofunctional compounds have a melting point above room temperature. Ithas been found that the oligomers derived from solid fluorochemicalmonofunctional compounds exhibit higher contact angle performance thanlower melting compounds.

[0103] Useful fluorine-containing monofunctional compounds includecompounds of the following formula III:

R_(f)−Q′  formula (II)

[0104] wherein:

[0105] R_(f) is a a perfluoroalkyl group having 1 to 12 carbon atoms, ora perfluoroheteroalkyl group having 3 to about 50 carbon atoms with allperfluorocarbon chains present having 6 or fewer carbon atoms;

[0106] Q′ is a moiety comprising a functional group that is reactivetoward the terminal acyl (of the polyacyl compound) or hydroxyl groups(of the polyol).

[0107] It will be understood with reference to Formula I that thecompound R_(f)Q′ reacts with the polyol or acyl compounds to provide theterminal moiety R_(f)Q—

[0108] R_(f)Q′ may comprise fluorine-containing monoalcohols includingthe following: R_(f)SO₂N(CH₃)CH₂CH₂OH, CF₃(CF₂)₃SO₂N(CH₃)CH₂CH₂OH,CF₃(CF₂)₃SO₂N(CH₃)CH(CH₃)CH₂OH, CF₃(CF₂)₃SO₂N(CH₃)CH₂CH(CH₃)OH,R_(f)SO₂N(H)(CH₂)₂OH, R_(f)SO₂N(CH₃)(CH₂)₄OH, C₄F₉SO₂N(CH₃)(CH₂)₄OHC₆F₁₃SO₂N(CH₃)(CH₂)₄OH, R_(f)SO₂N(CH₃)(CH₂)₁₁OH,R_(f)SO₂N(C₂H₅)CH₂CH₂OH, CF₃(CF₂)₃SO₂N(C₂H₅)CH₂CH₂OH,C₆F₁₃SO₂N(C₂H₅)CH₂CH₂OH R_(f)SO₂N(C₂H₅)(CH₂)₆OH,R_(f)SO₂N(C₂H₅)(CH₂)₁₁OH, R_(f)SO₂N(C₃H₇)CH₂OCH₂CH₂CH₂OH,R_(f)SO₂N(CH₂CH₂CH₃)CH₂CH₂OH, R_(f)SO₂N(C₄H₉)(CH₂)₄OH,R_(f)SO₂N(C₄H₉)CH₂CH₂OH, C₃F₇CONHCH₂CH₂OH,2-(N-methyl-2-(4-perfluoro-(2,6-diethylmorpholinyl))perfluoroethylsulfonamido)ethanol,R_(f)CON(CH₃)CH₂CH₂OH, R_(f)CON(C₂H₅)CH₂CH₂OH, R_(f)CON(CH₃)(CH₂)₁₁OH,R_(f)CON(H)CH₂CH₂OH C₂F₅O(C₂F₄O)₃CF₂CONHC₂H₄OH,CF₃O(CF(CF₃)CF₂O)₁₋₃₆CF(CF₃)CH₂OH, C₂F₅O(CF(CF₃)CF₂O)₁₋₃₆CF(CF₃)CH₂OH,C₃F₇O(CF(CF₃)CF₂O)₁₋₃₆CF(CF₃)CH₂OH, C₄F₉O(CF(CF₃)CF₂O)₁₋₃₆CF(CF₃)CH₂OH,C₃F₇O(CF(CF₃)CF₂O)₁₂CF(CF₃)CH₂OH, CF₃O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH,C₂F₅O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH, C₃F₇O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH,C₄F₉O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH, n-C₄F₉OC₂F₄OCF₂CH₂OCH₂CH₂OHCF₃O(CF₂CF₂O)₁₁CF₂CH₂OH, R_(f)SO₂CH₂CH₂OH, R_(f)COOCH₂CH₂CH(CH₃)OHR_(f)COOCH₂CH₂OH, C₅F₁₁COOCH₂CH₂OH, R_(f)(CH₂)₁₁N(C₂H₅)CH₂CH₂OH,R_(f)CH₂OH, C₃F₇CH₂OH, Perfluoro(cyclohexyl)methanol C₄F₉CH₂CH₂OH,CF₃(CF₂)₅CH₂CH₂OH R_(f)CH₂CH₂SO₂N(CH₃)CH₂CH₂OH,CF₃(CF₂)₅CH₂CH₂SO₂N(CH₃)CH₂CH₂OH, CF₃(CF₂)₃CH₂CH₂SO₂N(CH₃)CH₂CH₂OH,R_(f)CH₂CH₂CH₂OH, R_(f)(CH₂)₂OH, R_(f)(CH₂)₂S(CH₂)₂OH,C₄F₉(CH₂)₂S(CH₂)₂OH, R_(f)(CH₂)₄S(CH₂)₂OH, R_(f)(CH₂)₂S(CH₂)₃OH,R_(f)(CH₂)₂SCH(CH₃)CH₂OH, R_(f)(CH₂)₄SCH(CH₃)CH₂OH,R_(f)CH₂CH(CH₃)S(CH₂)₂OH, R_(f)(CH₂)₂S(CH₂)₁₁OH,R_(f)(CH₂)₂S(CH₂)₃O(CH₂)₂OH, R_(f)(CH₂)₃O(CH₂)₂OH,R_(f)(CH₂)₃SCH(CH₃)CH₂OH, and R_(f)SO₂N(H)(C₂H₄)O—C(O)(CH₂)₅—OH

[0109] and the like, and mixtures thereof, wherein R_(f) is a aperfluoroalkyl group having 1 to 12 carbon atoms, or aperfluoroheteroalkyl group having 3 to about 50 carbon atoms with allperfluorocarbon chains present having 6 or fewer carbon atoms. Ifdesired, rather than using such alcohols, similar thiols can beutilized.

[0110] Preferred fluorine-containing monoalcohols include2-(N-methylperfluorobutanesulfonamido)ethanol;2-(N-ethylperfluorobutanesulfonamido) ethanol;2-(N-methylperfluorobutanesulfonamido)propanol;N-methyl-N-(4-hydroxybutyl)perfluorohexanesulfonamide;1,1,2,2-tetrahydroperfluorooctanol; 1,1-dihydroperfluorooctanol;C₆F₁₃CF(CF₃)CO₂C₂H₄CH(CH₃)OH; n-C₆F₁₃CF(CF₃)CON(H)CH₂CH₂OH;C₄F₉OC₂F₄OCF₂CH₂OCH₂CH₂OH; C₃F₇CON(H)CH₂CH₂OH;1,1,2,2,3,3-hexahydroperfluorodecanol;C₃F₇O(CF(CF₃)CF₂O)₁₋₃₆CF(CF₃)CH₂OH; CF₃O(CF₂CF₂O)₁₋₃₆CF₂CH₂OH;C₄F₉—SO₂NMeC₂H₄OH, and the like; and mixtures thereof.

[0111] The fluorochemical monofunctional compound, R_(f)Q′, may comprisederivatives (such as esters or acid halides) of fluorine-containingmonocarboxylic acids including (1) those having the formulaR_(f)(CH₂)_(n)(X)_(p)(CH₂)_(m)COOH, wherein R_(f) is as defined above, nand m are independently integers of 0 to 14 (preferably 0-8, morepreferably 0-4), X is divalent oxygen or sulfur, and p is an integer of0 or 1, and (2) those having the formula R_(f)QR′COOH, wherein R_(f) isas defined above, R′ is a divalent alkyl (straight chain or branched) orcycloalkyl radical having from 1 to about 12 carbon atoms (preferablyfrom 1 to about 8 carbon atoms, more preferably from 1 to about 4 carbonatoms), and the divalent linking group Q is —SO₂N(R″)— or —CON(R″)—wherein R″ is a monovalent alkyl (straight chain or branched),cycloalkyl, or aryl radical having from 1 to about 12 carbon atoms(preferably from 1 to about 8 carbon atoms, more preferably from 1 toabout 4 carbon atoms).

[0112] Representative examples of useful derivatives offluorine-containing monocarboxylic acids include perfluorobutanoic(C₃F₇COOH), perfluoroisobutanoic ((CF₃)₂CFCOOH), hydroperfluorobutanoic(C₃F₆HCOOH), perfluoropentanoic (C₄F₉COOH), hydroperfluoropentanoic(C₄F₈HCOOH), perfluorohexanoic (C₅F₁₁COOH), hydroperfluorohexanoic(C₅F₁₀HCOOH), perfluorcyclohexanyl carboxylic (C₆F₁₁COOH),perfluoroheptanoic (C₆F₁₃COOH), perfluoro(3-ethoxypropionic),perfluoro(3-propoxypropionic), perfluoro(3-butoxypropionic),perfluoro(3-pentoxypropionic), R_(f)[OCF(CF₃)CF₂]₁₋₆OCF(CF₃)COOH whereR_(f) is a perfluroalkyl group of 1-12 carbon atoms,4-(4-perfluoroisopropoxyperfluorobutyl) butanoic,4-(bis(perfluoroisopropyl)fluoromethoxy)perfluorobutanoic,12-(2-perfluoroisopropoxyperfluoroethyl)dodecanoic,6-(2-perfluorocyclobutoxyperfluoroethyl) hexanoic,4-(bis(perfluoroisopropyl)fluoromethoxy)perfluorobutanoic,4-(2-bis(perfluoroisopropyl)fluoromethoxyperfluoroethyl)butanoic,2-(N-(ethyl)perfluorobutanesulfonamido)acetic, and2-(N-(methyl)perfluorobutanesulfonamido)acetic, and the like, andmixtures thereof.

[0113] Preferred fluorine-containing monocarboxylic acids include2-(N-(ethyl)perfluorobutanesulfonamido)acetic,2-(N-(methyl)perfluorobutanesulfonamido) acetic, and the like, andmixtures thereof.

[0114] It will be understood, with respect to the above lists, that theterminal hydroxyl or carboxyl groups may be replaced with otherfunctional groups Q′ that are reactive with terminal acyl group (of thepolyacyl compounds) or hydroxyl groups (of the polyol) to form thelinking group Q of Formula I.

[0115] If desired, non-fluorinated monofunctional compounds, such asmonoalcohol(s) or monocarboxylic acid(s) can be utilized in addition tothe fluorine-containing monoalcohol(s) or monocarboxylic acid(s) as aportion of the total monoalcohol or monocarboxylic acid charge (forexample, in amounts up to about 50 mole percent of the total).

[0116] The most preferred ester oligomers comprises the condensationreaction product of one or more fluorinated polyols, an excess amount(relative to the polyol) of one or more diacyl compounds, and sufficientfluorinated monoalcohols to react with the terminal acyl groups. Suchmost preferred oligomers correspond to the Formula

R_(f)Q[C(O)—R¹—C(O)O—R²O—]_(n)[C(O)—R¹—C(O)]_(m)—QR_(f)

[0117] wherein:

[0118] n is a number from 1 to 10 inclusive;

[0119] m is 1;

[0120] R_(f) is a perfluoroalkyl group having 1 to 12, preferably 6 orfewer carbon atoms, or a perfluoroheteroalkyl group having 3 to about 50carbon atoms with all perfluorocarbon chains present having 1 to 6,preferably 1 to 4 carbon atoms;

[0121] Q is a divalent linking group as previously described;

[0122] R¹ is a straight chain alkylene, of 1 to 14 carbon atoms.Optionally, R¹ may further comprise a water-solubilizing group or apolymerizable group;

[0123] R₂ is a polyvalent organic group which is a residue of thepolyol, that is a straight or branched chain alkylene, cycloalkylene,arylene or heteroalkylene group of 1 to 14 carbon atoms, preferably 1 to8 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferablytwo carbon atoms, or an arylene group of 6 to 12 carbon atoms; at leasta portion of R² groups are substituted with or contain oneperfluoroalkyl group, perfluoroheteroalkyl group,perfluoroheteroalkylene group, or mixtures thereof. Optionally, R² mayfurther comprise a water-solubilizing group or a polymerizable group.

[0124] The fluorochemical compositions may further comprise the reactionproduct of water-solubilizing compounds comprising one or morewater-solubilizing groups and at least one group reactive with thehydroxy (of the polyol) or the acyl group (of the polyacyl compound).

[0125] The water-solubilizing groups of the water solubilizing compoundsinclude, for example, carboxylate, sulfate, sulfonate, phosphate,phosphonate, ammonium, and quaternary ammonium groups. Such groups maybe represented as —CO₂M, —OSO₃M, —SO₃M, —PO(OM)₂, —P(OM)₃, —NR₂HX,—NR₃X, —NRH₂X, and —NH₃X, respectively, wherein M is H or one equivalentof a monovalent or divalent soluble cation such as sodium, potassium,calcium, and NR₃H⁺; X is a soluble anion such as those selected from thegroup consisting of halide, hydroxide, carboxylate, sulfonates, and thelike; and R is selected from the group consisting of a phenyl group, acycloaliphatic group, or a straight or branched aliphatic group havingfrom about 1 to about 12 carbon atoms. Preferably, R is a lower alkylgroup having from 1 to 4 carbon atoms. The group —NR₃X is a salt of awater-soluble acid, for example trimethyl ammonium chloride, pyridiniumsulfate, etc. or an ammonium substituent. The group —NR₂HX is the saltof a water-soluble acid, such as dimethyl ammonium acetate orpropionate. The group —NRH₂X is the salt of a water-soluble acid, suchas methyl ammonium acetate or propionate. The group —NH₃X is the salt ofa water-soluble acid, such as ammonium acetate or propionate. The saltform can be made by simple neutralization of the acid group with a basesuch as an amine, a quaternary ammonium hydroxide, an alkali metalcarbonate or hydroxide, or the like; or alternatively by simple reactionof the amino group with a carboxylic acid, a sulfonic acid, a halo acid,or the like.

[0126] The water solubilizing group is incorporated into thefluorochemical ester compounds by means of a reactive group which isreactive with the hydroxy (of the polyol) or the acyl group (of thepolyacyl compound).

[0127] Useful acyl reactive groups include those selected from the groupconsisting of —OH, —SH, NH₂, and NRH wherein R is selected from thegroup consisting of a phenyl group, a cycloaliphatic group, or astraight or branched aliphatic group having from about 1 to about 12carbon atoms. Preferably, R is a lower alkyl group having from 1 to 4carbon atoms. A representative suitable diol with a solubilizing groupis 1,1-bis(hydroxymethyl)propionic acid and its salts such as itsammonium salt. A representative suitable monoalcohol with a solubilizinggroup is glycolic acid (HOCH₂COOH) and its salts. The amount ofwater-solubilizing group should be sufficient to solubilize or allowdispersion of the fluorochemical composition. Typically, theester:solubilizing group ratio should be from about 3:1 to about 16:1,preferably from about 5:1 to about 11:1. Similarly, thewater-solubilizing group may be incorporated into the fluorochemicalurethane oligomers by means of a hydroxyl-reactive group, such aselectrophilic functional groups, as known in the art.

[0128] Illustrative water-solubilizing compounds having suitablewater-solubilizing groups include, but are not limited to, thoseindependently selected from the group consisting of HOCH₂COOH;HSCH₂COOH; (HOCH₂CH₂)₂NCH₂COOH; HOC(CO₂H)(CH₂CO₂H)₂;(H₂N(CH₂)_(n)CH₂)₂NCH₃ wherein n is an integer of 1 to 3;(HOCH₂)₂C(CH₃)COOH; (HO(CH₂)_(n)CH₂)₂NCH₃ wherein n is an integer of 1to 3; HOCH₂CH(OH)CO₂Na; N-(2-hydroxyethyl)iminodiacetic acid(HOCH₂CH₂N(CH₂COOH)₂); L-glutamic acid (H₂NCH(COOH)(CH₂CH₂COOH));aspartic acid (H₂NCH(COOH)(CH₂COOH)); glycine (H₂NCH₂COOH);1,3-diamino-2-propanol-N,N,N′,N′-tetraacetic acid(HOCH(CH₂N(CH₂COOH)₂)₂); iminodiacetic acid (HN(CH₂COOH)₂);mercaptosuccinic acid (HSCH(COOH)(CH₂COOH));H₂N(CH₂)₄CH(COOH)N(CH₂COOH)₂; HOCH(COOH)CH(COOH)CH₂COOH;(HOCH₂)₂CHCH₂COO)⁻(NH(CH₃)₃)⁺; CH₃(CH₂)₂CH(OH)CH(OH)(CH₂)₃CO₂K;H₂NCH₂CH₂OSO₃Na; H₂NC₂H₄NHC₂H₄SO₃H; H₂NC₃H₆NH(CH₃)C₃H₆SO₃H;(HOC₂H₄)₂NC₃H₆OSO₃Na; (HOCH₂CH₂)₂NC₆H₄OCH₂CH₂OSO₂OH;N-methyl-4-(2,3-dihydroxypropoxy)pyridinium chloride,((H₂N)₂C₆H₃SO₃)⁻(NH(C₂H₅)₃)⁺; dihydroxybenzoic acid;3,4-dihydroxybenzylic acid; 3-(3,5-dihydroxyphenyl)propionic acid; saltsof the above amines, carboxylic acids, and sulfonic acids; diol-aminesof the general formula R—N[(CH₂CH₂O)_(x)H[(CH₂CH₂O)y]H, where x+y=2, 5,10, 15 and 50, triol-amines of the general formulaR—N[(CH₂CH₂O)x]H—CH₂CH₂CH₂—N[(CH₂CH₂O)y]H[CH₂CH₂O)_(z)H], where x+y+z=3,10, 15 and 50,and ammonium salts of the indicated triol- and diol-amines(where R is an alkyl, available from Akzo Chemical; acrylic andmethacrylic acid; and mixtures thereof. An example of awater-solubilizing compound having a hydroxy-reactive functional groupis Br—(CH₂)_(n)—CO₂H.

[0129] The fluorochemical compositions may further comprise the reactionproduct of polymerizable compounds comprising one or more polymerizablegroups and at least one reactive group, reactive with hydroxyl or acylgroups. The polymerizable group may be incorporated into thefluorochemical ester oligomers by means of a reactive functional group,as previously described. Examples of useful polymerizable groups includebut are not limited to acrylate, methacrylate, vinyl, allyl, andglycidyl. Representative useful compounds having polymerizable groupsinclude hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythrioltriacrylate, allyl alcohol, glycidol, C₂H₅(CH₃)C═N—OH, CH₂═CHO(CH₂)₄OHand glycidyl methacrylate.

[0130] The fluorochemical compositions of the present inventioncomprising a mixture of ester molecules can be made by simple blendingof the polyol(s), monofunctional compound(s), polyacyl compound(s) andoptionally (d) one or more water-solubilizing compounds or (e) one ormore polymerizable compounds. As one skilled in the art wouldunderstand, the order of blending or the ordering of the steps isnon-limiting and can be modified so as to produce a desiredfluorochemical composition. In the synthesis, for example, the polyacylcompound(s), the polyol(s), the fluorine-containing monofunctionalcompound (R_(f)Q′), and optionally (d) one or more water-solubilizingcompounds or (e) one or more polymerizable compounds and a solvent arecharged to a dry reaction vessel in immediate succession or as pre-mademixtures. When a homogeneous mixture or solution is obtained a catalystis typically added, and the reaction mixture is heated. The temperatureis generally determined by the boiling point of the solvent, and theboiling point of the byproducts. Byproducts, such as water or alcoholsare generally removed by azeotropic distillation.

[0131] When a fluorine-containing monofunctional compound (R_(f)Q′) isused to prepare fluorine-containing ester compounds and oligomers ofFormula I above, the molar ratio of monofunctional compound to polyacylcompound can be in the range of about 1:1 to 1:10 (preferably, about 1:1to 1:7; more preferably, about 1:1 to 1:2; and most preferably, about1:1 to 1:1.5). The ratio of polyacyl compound to polyol can then be inthe range of about 2:1 to 1:2. Preferably, the ratio of the total numberof equivalents of hydroxyl groups to the total number of equivalents ofacyl groups is about 1:1. A slight excess of either the polyacylcompound or polyol is preferred.

[0132] Depending on reaction conditions (e.g., reaction temperatureand/or polyacyl compound used), a catalyst level of up to about 0.5percent by weight of the polyacyl compound /polyol/monofunctionalcompound mixture may be used, but typically about 0.00005 to about 0.5percent by weight is required, 0.02 to 0.1 percent by weight beingpreferred. Suitable catalysts include, those acid and baseesterification catalysts such as are known in the art. Useful catalystsinclude Me—Ph—SO₃H and CF₃SO₃H. If an acid catalyst is used, it ispreferably removed from the oligomer or neutralized after theoligomerization. It has been found that the presence of the catalyst maydeleteriously affect the contact angle performance.

[0133] A mixture of polyols and/or a mixture of monofunctional compoundscan be used instead of a single polyol and/or a single monofunctionalcompound. For example, a polyol mixture comprising a polyol with awater-solubilizing or a polymerizable group and a polyol with an R_(f)group can be used. As well, a monofunctional compound mixture comprisinga monofunctional compound with a water-solubilizing or polymerizablegroup and a fluorine-containing monofunctional compound can be used.

[0134] The fluorochemical compositions of the invention can be preparedby using procedures and apparatus known to those skilled in the art ofesterification and ester exchange reactions. For example, thefluorochemical compositions can be prepared by (a) simultaneouslyreacting the fluorine-containing monofunctional compound with the polyoland the diacyl compound (or derivative); (b) first reacting the polyolwith the polyacyl compound (or derivative), and then reacting theresulting mixture with the fluorine-containing monofunctional compound;or (c) first reacting either the fluorine-containing monofunctionalcompound with the diacyl compound (or derivative) or thefluorine-containing monofunctional compound with the polyol, and thenreacting the resulting mixture with the remaining reactant. Method (b)is generally preferred, because the probability of complete consumptionof the fluorine-containing reactant can be higher than for Methods (a)and (c), and because it is believed that this method can produce abroader range of oligomers than Methods (a) and (c).

[0135] The reactions can be carried out in solution or in the moltenstate (using commonly-used solvents and/or equipment), generally underatmospheric pressure and at temperatures sufficient to maintain thereactants in solution or in the melt. For example, melt temperatures inthe range of about 90-240° C. (preferably, about 100-210° C.; morepreferably, about 110-170° C.) can generally be utilized. Removal ofsolvent or byproduct HCl, if present, can be conducted at reducedpressures, for example, using a vacuum equivalent to 500 torr (67 kPa)or less. Removal of esterification byproducts by distillation may beeffect by selection of an appropriate solvent, such as toluene orfluorinated ethers such as HFE-7100™ or HFE-7200™ (available from the 3MCompany).

[0136] If water is a by-product, then water immiscible solvents such astoluene, fluorinated ethers or perfluorocarbons are preferred. If thebyproducts are lower alcohols, then perfluorocarbons are preferred.

[0137] The fluorochemical compositions of the present inventioncomprising a mixture of ester compounds can also be made following astep-wise synthesis in addition to a batch method. In the synthesis, thepolyacyl compound and the polyol are dissolved together under dryconditions, preferably in a solvent, and then the resulting solution isheated as previously described, with mixing in the presence of acatalyst for one-half to two hours, preferably one hour.

[0138] The resulting ester oligomers may then further reacted with oneor more of the monofunctional compounds described above. Themonofunctional compounds may be added to the above reaction mixture, andreact(s) with the remaining or a substantial portion of the remaininghydroxyl or acyl groups. The above temperatures, dry conditions, andmixing are continued one-half to two hours, preferably one hour.Terminal fluorine-containing groups may thereby bonded to the hydroxylor acyl functional ester oligomers and compounds. These oligomers andcompounds can be optionally further functionalized withwater-solublizing or polymerizable groups described above by reactingany of the remaining hydroxyl or acyl groups in the resulting mixturewith one or more of the reactive water-solubilizing or polymerizablegroup-containing compounds described above. Thus, the water-solubilizingor polymerizable compound(s) is (are) added to the reaction mixture,using the same conditions as with the previous additions.

[0139] Water-solubilizing or polymerizable group-containing compoundscan be added and reacted with hydroxyl or acyl groups under theconditions described above in any of the steps described above. Forexample, as mentioned above, the water-solubilizing or polymerizablegroup-containing compound can be added as a mixture with the polyol.Alternatively, the water-solubilizing or polymerizable group-containingcompound can be added (a) after reaction of the polyol with the polyacylcompound, (b) as a mixture with the monoalcohol(s), and (c) afterreaction of the polyol and monofunctional compound with the polyacylcompound. When the water-solubilizing or polymerizable group-containingcompound is a monoalcohol, it is preferably added as a mixture with thefluorine-containing monoalcohol. When the water-solubilizing orpolymerizable group-containing compound is a diol, it is preferablyadded as a mixture with the polyol.

[0140] When the chemical composition of the present invention containsan ester oligomer having one or more carboxylic acid groups, solubilityor dispersability of the composition in water can be further increasedby forming a salt of the carboxylic acid group(s). Basic salt-formingcompounds, such as tertiary amines, quaternary ammonium hydroxides, andinorganic bases, including, but not limited to, those selected from thegroup consisting of sodium hydroxide, potassium hydroxide, cesiumhydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide,zinc hydroxide, and barium hydroxide, may be used in a sufficient amount(i.e., in an amount to maintain a pH of greater than about 6). Thesebasic salt-forming compounds preferably can be added in the water phase,but optionally in the preparation of the ester oligomers, to form saltswith the incorporated, pendant and/or terminal carboxylic acid groups onthe ester oligomer. Examples of useful amine salt-forming compoundsinclude, but are not limited to, those selected from the groupconsisting of ammonia, trimethyl amine, triethyl amine, tripropylamine,triisopropyl amine, tributylamine, triethanolamine, diethanolamine,methyldiethanolamine, morpholine, N-methylmorpholine,dimethylethanolamine, and mixtures thereof. Preferred salt formingcompounds include those selected from the group consisting of ammonia,trimethylaamine, dimethylethanolamine, methyldiethanolamine,triethylamine, tripropylamine, and triisopropylamine, since the chemicalcompositions prepared therefrom are not excessively hydrophilic uponcoating and curing. Since certain salts formed by the reaction of saltforming compounds, such as potassium hydroxide in combination with acarboxylic acid group, could result in undesired reaction with acylgroups, it is preferred to add the salt forming compound in a waterphase after all of the diols, alcohol, and silane compounds have beenreacted with the acyl groups of the polyacyl compound.

[0141] If desired for particular applications, small amounts of one ormore polymeric or non-polymeric chain extenders (for example, diamines)can be utilized, in addition to the above-described reactants, inpreparing the fluorochemical composition.

[0142] The coating compositions of the present invention compriseaqueous suspensions, emulsions, or solutions, or organic solvent (ororganic solvent/water) solutions, suspensions, or emulsions comprisingthe fluorochemical compositions of the present invention. When appliedas coatings, the fluorochemical coating compositions impart oil- andwater-repellency properties, and/or stain-release and stain-resistancecharacteristics to any of a wide variety of substrates.

[0143] The fluorochemical compositions of the present invention can bedissolved, suspended, or dispersed in a variety of solvents to formcoating compositions suitable for use in coating the chemicalcompositions of the present invention onto a substrate. Generally, thesolvent solutions can contain from about 0.1 to about 50 percent, oreven up to about 90 percent, by weight non-volatile solids (based on thetotal weight of the components). Aqueous suspensions, emulsions, orsolutions are generally preferred and generally can contain anon-volatile solids content of about 0.1 to about 50 percent,preferably, about 1 to about 10 percent, by weight (based on the totalweight of the components). Coating compositions preferably contain fromabout 0.1 to about 10 percent fluorochemical composition, based on theweight of the coating composition. Preferably the fluorochemicalcomposition is used in the coating composition at about 1 to about 5weight percent, most preferably from about 2 to about 3 weight percent.Suitable solvents include water, alcohols, esters, glycol ethers,amides, ketones, hydrocarbons, chlorohydrocarbons, hydrofluorocarbons,hydrofluoroethers, chlorocarbons, and mixtures thereof. Depending uponthe substrate to which the composition is being applied, water is thepreferred solvent because it does not raise any environmental concernsand is accepted as safe and non-toxic.

[0144] Another embodiment of the present invention is an articlecomprised of a substrate having one or more surfaces and on the one ormore surfaces of this substrate is a cured coating derived from thecoating composition of the present invention. After application andcuring of the coating composition, the article displays high water andhexadecane dynamic receding contact angles, oil- and water-repellency,and/or stain-release and stain-resistance properties.

[0145] The coating compositions of the present invention can be appliedto a wide variety of substrates, including, but not limited to, fibroussubstrates and hard substrates. Fibrous substrates include woven, knit,and nonwoven fabrics, textiles, carpets, leather, and paper. Hardsubstrates include, but are not limited to, glass, ceramic, masonry,concrete, natural stone, man-made stone, metals, wood, plastics, andpainted surfaces. Substrates can have flat or curved surfaces and may beparticulate and fibrous in nature, as well. Preferred substrates arefibrous or are capable of imbibing a liquid and are therefore porous.Such substrates are particularly subject to staining and soiling, butalso benefit greatly from the fluorochemical compositions of the presentinvention because the coating composition can penetrate into the fibrousor porous substrate surface and spread over the internal surfaces of thesubstrate.

[0146] Representative examples of substrates that can be coated with thecoating composition include lenses used in ophthalmic spectacles,sunglasses, optical instruments, illuminators, watch crystals, and thelike; plastic window glazing; signs; decorative surfaces such aswallpaper and vinyl flooring; composite or laminated substrates such asFORMICA™ brand sheeting or laminated flooring (e.g., PERGO™ brandflooring); ceramic tile and fixtures (sinks, showers, toilets); naturaland man-made stones; decorative and paving stones; cement and stonesidewalks and driveways; particles that comprise grout or the finishedsurface of applied grout; wood furniture surface (desktops, tabletops);cabinet surfaces; wood flooring, decking, and fencing; leather; paper;fiber glass fabric and other fiber-containing fabrics; textiles;carpeting; drapery material, upholstery, clothing, and the like.

[0147] Since coatings prepared from the coating compositions can rendermetal surfaces resistant to soils, the optical properties of metalsurfaces like those on decorative metal strips and mirrors can bepreserved longer. The coating compositions can make wood surfaces moreresistant to food and beverage stains while helping to maintain alustrous appearance. In addition, the coating compositions can beapplied as a protective coating on aircraft wings, boat hulls, fishingline, medical surfaces, and siding, and can be used in food release,mold release, adhesive release applications, and the like. Decorativestones include, for example, marble, granite, limestone, slate, and thelike.

[0148] Preferred substrates that can be coated with the coatingcomposition of the present invention are fibrous substrates, such asnonwoven, knits, and woven fabrics, carpet, drapery material,upholstery, clothing and essentially any textile. To impart repellencyand/or stain-resistance characteristics to a substrate, having one ormore surfaces, (a) the coating composition of the present invention isapplied onto one or more surfaces of the substrate and (b) the coatingcomposition is allowed to cure (i.e. dry) at ambient temperature orpreferably at elevated temperatures. The use of elevated temperatures isparticularly advantageous for curing fibrous substrates coated with thefluorochemical compositions of the present invention, since bestrepellency properties are then achieved. Elevated temperatures of 50 to150° C. are preferred with 100 to 130° C. more preferred.

[0149] The coating compositions can be applied to a treatable substrateby standard methods such as, for example, spraying, padding, dipping,roll coating, brushing, or exhaustion (optionally followed by the dryingof the treated substrate to remove any remaining water or solvent). Thetreatable substrate can be in the form of molded or blown articles,sheets, fibers (as such or in aggregated form, for example, yam, toe,web, or roving, or in the form of fabricated textiles such as carpets),woven and nonwoven fabrics, films, etc. When coating flat substrates ofappropriate size, knife-coating or bar-coating may be used to ensureuniform coatings of the substrate. If desired, the fluorochemicalcomposition can be co-applied with conventional fiber treating agents,for example, spin finishes or fiber lubricants. Such a topical treatmentprocess can involve the use of the neat fluorochemical composition,without added solvent, and is thus preferred from an environmentalperspective over the use of organic solvent solutions of thefluorochemical composition.

[0150] The coating compositions can be applied in an amount sufficientto achieve the desired repellency properties for a particularapplication. This amount can be determined empirically and can beadjusted as necessary or desired to achieve the repellency propertieswithout compromising the properties of the treatable substrate.

[0151] The coating compositions can be applied to a substrate in anydesired thickness. Coatings as thin as a few microns can offer excellentlow surface energy, stain-resistance, and stain-release. However,thicker coatings (e.g., up to about 20 microns or more) can also beused. Thicker coatings can be obtained by applying to the substrate asingle thicker layer of a coating composition that contains a relativelyhigh concentration of the chemical composition of the present invention.Thicker coatings can also be obtained by applying successive layers tothe substrate of a coating composition that contains a relatively lowconcentration of the fluorochemical composition of the presentinvention. The latter can be done by applying a layer of the coatingcomposition to the substrate and then drying prior to application of asuccessive layer. Successive layers of the coating can then be appliedto dried layers. This procedure can be repeated until the desiredcoating thickness is achieved.

[0152] Another embodiment of the present invention is a water- andoil-repellent polymer composition prepared by (a) combining therepellency-imparting, fluorochemical composition and at least onethermoplastic polymer (optionally, along with other additives) and thenmelt processing the resulting combination; or (b) combining therepellency-imparting, fluorochemical composition and at least onethermosetting polymer or ceramer or the reactive precursors thereof(optionally, along with other additives) and then curing the resultingcombination, optionally with the application of heat or actinicradiation. Alternative processes for preparing the polymer compositioninclude, for example, (c) dissolving the repellency-imparting,fluorochemical composition and at least one treatable substrate (e.g., apolymer) in at least one solvent and then casting or coating (forexample, on a substrate such as plastic sheet or film, fabric, wood,ceramic, or stone) the resulting solution and allowing evaporation ofthe solvent, optionally with the application of heat; and (d) combiningthe repellency-imparting, fluorochemical composition and at least onemonomer (optionally, along with other additives) and then polymerizingthe monomer, optionally in the presence of at least one solvent andoptionally with the application of heat or actinic radiation.

[0153] To form a polymer melt blend by melt processing, thefluorochemical composition can be, for example, intimately mixed withpelletized or powdered polymer and then melt processed by known methodssuch as, for example, molding, melt blowing, melt spinning, or meltextrusion. The fluorochemical composition can be mixed directly with thepolymer or it can be mixed with the polymer in the form of a “masterbatch” (concentrate) of the fluorochemical composition in the polymer.If desired, an organic solution of the fluorochemical composition can bemixed with powdered or pelletized polymer, followed by drying (to removesolvent) and then by melt processing. Alternatively, the fluorochemicalcomposition can be injected into a molten polymer stream to form a blendimmediately prior to, for example, extrusion into fibers or films ormolding into articles.

[0154] After melt processing, an annealing step can be carried out toenhance the development of repellent characteristics. In addition to, orin lieu of, such an annealing step, the melt processed combination (forexample, in the form of a film or a fiber) can also be embossed betweentwo heated rolls, one or both of which can be patterned. An annealingstep typically is conducted below the melt temperature of the polymer(for example, in the case of polyamide, at about 150-220° C. for aperiod of about 30 seconds to about 5 minutes).

[0155] The fluorochemical composition can be added to thermoplastic orthermosetting polymer (or, alternatively, to other treatable substratematerials) in amounts sufficient to achieve the desired repellencyproperties for a particular application. The amounts can be determinedempirically and can be adjusted as necessary or desired to achieve therepellency properties without compromising the properties of the polymer(or other treatable substrate material). Generally, the fluorochemicalcomposition can be added in amounts ranging from about 0.1 to about 10percent by weight (preferably, from about 0.5 to about 4 percent; morepreferably, from about 0.75 to about 2.5 percent) based on the weight ofpolymer (or other treatable substrate material).

[0156] Shaped articles can be made from the water- and oil-repellentcomposition of the invention, and such constructions will find utilityin any application where some level of repellency characteristics isrequired. For example, the composition of the invention can be used toprepare films and molded or blown articles, as well as fibers (forexample, melt-blown or melt-spun fibers, including microfibers andsheath-core fibers) that can be used to make woven, knit, and nonwovenfabrics. Such films, molded or blown articles, fibers, and fabricsexhibit water and oil repellency (and soil resistance) characteristicsunder a variety of environmental conditions and can be used in a varietyof applications.

[0157] For example, molded articles comprising the composition of theinvention can be prepared by standard methods (for example, by hightemperature injection molding) and are particularly useful as, forexample, headlamp covers for automobiles, lenses (including eyeglasslenses), casings or circuit boards for electronic devices (for example,computers), screens for display devices, windows (for example, aircraftwindows), and the like. Films comprising the composition of theinvention can be made by any of the film making methods commonlyemployed in the art. Such films can be nonporous or porous (the latterincluding films that are mechanically perforated), with the presence anddegree of porosity being selected according to the desired performancecharacteristics. The films can be used as, for example, photographicfilms, transparency films for use with overhead projectors, tapebackings, substrates for coating, and the like.

[0158] Fibers comprising the composition of the invention can be used tomake woven, knit, or nonwoven fabrics that can be used, for example, inmaking medical fabrics, medical and industrial apparel, fabrics for usein making clothing, home furnishings such as rugs or carpets, papermachine clothing, and filter media such as chemical process filters orrespirators. Nonwoven webs or fabrics can be prepared by processes usedin the manufacture of either melt-blown or spunbonded webs. For example,a process similar to that described by Wente in “Superfine ThermoplasticFibers,” Indus. Eng'g Chem. 48, 1342 (1956) or by Wente et al. in“Manufacture of Superfine Organic Fibers,” Naval Research LaboratoriesReport No. 4364 (1954) can be used. Multi-layer constructions made fromnonwoven fabrics enjoy wide industrial and commercial utility, forexample, as medical fabrics. The makeup of the constituent layers ofsuch multi-layer constructions can be varied according to the desiredend-use characteristics, and the constructions can comprise two or morelayers of melt-blown and spunbonded webs in many useful combinationssuch as those described in U.S. Pat. Nos. 5,145,727 (Potts et al.) and5,149,576 (Potts et al.), the descriptions of which are incorporatedherein by reference. In multi-layer constructions, the fluorochemicalcomposition can be used alone in one or more layers or can be used incombination with other additive(s) in one or more layers. Alternatively,the fluorochemical composition and the other additive(s) can each beindependently segregated in one or more layers. For example, in aspunbonded/melt-blown/spunbonded (“SMS”) three-layer construction, theother additive(s) (for example, antistats) can be used in one or bothspunbonded layers, and the fluorochemical composition can be used in themelt-blown layer, to impart both antistatic and repellencycharacteristics to the overall construction.

[0159] The repellency-imparting, fluorochemical polymer composition canalso find utility as an additive to coatings. Such coatings can bewater- and oil-repellent, and scratch-resistant (as well assoil-resistant) and can be used in the photographic industry or asprotective coatings for optical or magnetic recording media.

[0160] If desired, the water- and oil-repellent composition of theinvention can further contain one or more additives, including thosecommonly used in the art, for example, dyes, pigments, antioxidants,ultraviolet stabilizers, flame retardants, surfactants, plasticizers,tackifiers, fillers, and mixtures thereof. In particular, performanceenhancers (for example, polymers such as polybutylene) can be utilizedto improve the repellency characteristics in, for example, melt additivepolyolefin applications.

[0161] Objects and advantages of this invention are further illustratedby the following examples, but the particular materials and amountsthereof recited in these examples, as well as other conditions anddetails, should not be construed to unduly limit this invention. In theexamples, where weight percent or parts by weight are indicated, theseare based on the weight of the entire composition unless indicatedotherwise.

EXAMPLES

[0162] Glossary

[0163] POSF—C₈F₁₇SO₂F, perfluorooctanesulfonyl fluoride, available asFLUORAD™ FX-8 fluorochemical intermediate from 3M Company, St. Paul,Minn.

[0164] PHSF—C₆F₁₃SO₂F, perfluorooctanesulfonyl fluoride, available as afluorochemical intermediate from 3M Company.

[0165] PBSF—C₄F₉SO₂F, perfluorobutanesulfonyl fluoride, available fromSigma-Aldrich, Milwaukee, Wis.

[0166] MeFOSE—C₈F₁₇SO₂N(CH₃)CH₂CH₂OH, having an equivalent weight of557, can be made in two stages by reacting POSF with methylamine andethylenechlorohydrin, using a procedure essentially as described inExample 1 of U.S. Pat. No. 2,803,656 (Ahlbrecht et al.), oralternatively by reacting N-methylperfluorooctylsulfonamide withethylene glycol carbonate, using the procedure essentially as describedin Example 7 of U.S. Pat. No. 3,734,962 (Niederprum et at.).

[0167] MeFBSE—C₄F₉SO₂N(CH₃)CH₂CH₂OH, having an equivalent weight of 357,can be made in two stages by reacting PBSF with methylamine andethylenechlorohydrin, using a procedure essentially as described inExample 1 of U.S. Pat. No. 2,803,656 (Ahlbrecht, et al.).

[0168] FOSEE—C₈F₁₇SO₂N(C₂H₄OH)₂, can be prepared by reacting C₈F₁₇SO₂NH₂with ethylene chlorohydrin as described in Example 8 of U.S. Pat. No.3,787,351 (Olson). C₈F₁₇SO₂NH₂ can be prepared by reacting POSF with anequimolar amount of NH₃.

[0169] FHSEE—C₆F₁₃SO₂N(C₂H₄OH)₂, can be prepared as described in Example8 of U.S. Pat. No. 3,787,351 (Olson), except that an equimolar amount ofC₆F₁₃SO₂NH₂ is substituted for C₈F₁₇SO₂NH₂. C₆F₁₃SO₂NH₂ can be preparedby reacting PHSF with an equimolar amount of NH₃.

[0170] FBSEE—C₄F₉SO₂N(C₂H₄OH)₂, can be prepared as described in Example8 of U.S. Pat. No. 3,787,351 (Olson), except that an equimolar amount ofC₄F₉SO₂NH₂ is substituted for C₈F₁₇SO₂NH₂. C₄F₉SO₂NH₂ can be prepared byreacting PBSF with an equimolar amount of NH₃.

[0171] HDO—hexanediol, HO(CH₂)₆OH, available from Sigma-Aldrich.

[0172] ADA—adipic acid, HOOC(CH₂)₄COOH, available from Sigma-Aldrich.

[0173] ADC—adipoyl chloride, ClC(O)(CH₂)₄C(O)Cl, available fromSigma-Aldrich.

[0174] SBA—suberic acid, HOOC(CH₂)₆COOH, available from Sigma-Aldrich.

[0175] AZA—azelaic acid, HOOC(CH₂)₇COOH, available from Sigma-Aldrich.

[0176] DDA—dodecanedioic acid, HOOC(CH₂),₁₀COOH, available fromSigma-Aldrich.

[0177] AA—acrylic acid, CH₂═CHCOOH, available from Sigma-Aldrich.

[0178] CA—citric acid, HOOCCH₂CH(OH)(COOH)CH₂COOH, 99+%, available fromSigma-Aldrich.

[0179] Dimer Acid—hydrogenated dimmer acid available from Aldrich.

[0180] PEG Diacid—HOOCCH₂(OCH₂CH₂)_(n)OCH₂COOH, molecular weightapproximately 600, available from Aldrich.

[0181] pTSA—p-toluenesulfonic acid monohydrate, available fromSigma-Aldrich.

[0182] CF₃SO₃H—trifluoromethanesulfonic acid, available as FLUORAD™FC-24 fluorochemical acid from 3M Company.

[0183] VAZO™ 64—2,2′-azobis(isobutyronitrile) initiator, available fromE. I. duPont de Nemours, Wilmington, Del.

[0184] THF—tetrahydrofuran

[0185] EtOAc—ethyl acetate

[0186] TEST METHODS

[0187] Stain Test—Zanger Blue limestone tiles (available from ColorTile, Maplewood, Minn.) (30.5 cm by 30.5 cm by 1.0 cm thick) weredivided into 6 sections (10.2 cm by 15.2 cm) and washed with waterthoroughly and allowed to dry at room temperature overnight. A 5%solvent solution of the polyester of the invention to be evaluated wascoated onto the surface by wiping twice with a paper towel saturatedwith the chemical composition. Each of the resulting treated tilesections was then allowed to dry at ambient laboratory temperature forat least 12 hours before testing.

[0188] A spot test was used to visually rate the ability of the treatedtile sections to prevent a test fluid drop from staining the tile aftera given exposure period. The following test fluids were used:

[0189] (1) Grape juice (GJ)

[0190] (2) Anti-freeze coolant (AFC)

[0191] (3) Used 10W30 motor oil (MO)

[0192] (4) Paul Masson™ Burgundy wine (WIN)

[0193] (5) Water saturated with Taster's Choice coffee (COF)

[0194] (6) STP™ heavy duty brake fluid (BF)

[0195] (7) Mazola™ corn oil (CO)

[0196] (8) Soy sauce(SS)

[0197] A drop of each of the test fluids was place on each of thetreated tile sections. After 20-24 hours, the drops were removed bywiping with a clean, dry, paper towel, and the tile was washed andscrubbed with Dawn™ liquid dishwashing soap mixed at 6 weight percentwith tap water and rinsed with tap water. The visual appearance of thespot where each drop of test fluid had been place was rated on a scaleof 0-5 as shown below. A rating of 0 represented the best stain-releaseperformance of a chemical composition treatment of the tile surface.

[0198] 0=no visible stain

[0199] 1=trace of stain visible

[0200] 2=outline of drop barely visible

[0201] 3=outline of drop visible

[0202] 4=dark outline of drop

[0203] 5=dark stain which has spread

[0204] A total rating summing the eight stain tests was also calculatedto provide an overall stain resistance rating for the treated substrate.A smaller total rating indicates a more effective treatment.

[0205] Advancing and Receding Contact Angle Test—The Advancing andReceding Contact Angle Test provides a quick and precise prediction ofthe surface properties of a coating material . Advancing and Recedingcontact angle values measured with water and n-hexadecane using thistest correlate well with fluid repellency values measured on fabrics andcarpets.

[0206] To run this test, a solution, emulsion, or suspension (typicallyat about 3% solids) is applied to nylon film by dip-coating. The nylonfilm is prepared as follows. Nylon film is cut into 85 mm×13 mmrectangular strips. Each strip is cleaned by dipping into methylalcohol, wiping with a KIMWIPE™ wiper (commercially available fromKimberly-Clark Corp., Neenah, Wis.), taking care not to touch thestrip's surface, and allowing the strip to dry for 15 minutes. Then,using a small binder clip to hold one end of the strip, the strip isimmersed in the treating solution, and the strip is then withdrawnslowly and smoothly from the solution. The coated film strip is tiltedto allow any solution run-off to accumulate at the corner of the strip,and a KIMWIPE™ wiper is touched to the corner to pull away the solutionbuildup. The coated film strip is allowed to air dry in a protectedlocation for a minimum of 30 minutes and then is cured for 10 minutes at121° C.

[0207] After the treatment is dry and cured, the advancing and recedingcontact angles are measured using a CAHN Dynamic Contact Angle Analyzer,Model DCA 322 (a Wilhelmy balance apparatus equipped with a computer forcontrol and data processing, commercially available from ATI, Madison,Wis.). The CAHN Dynamic Contact Angle Analyzer is calibrated using a 500mg weight. An alligator clip is fastened to a piece of coated film stripabout 30 mm long, and the clip and film piece are hung from the stirrupof the balance. A 30 mL glass beaker containing approximately 25 mL ofwater or n-hexadecane is placed under the balance stirrup, and thebeaker is positioned so that the coated film strip is centered over thebeaker and its contents but not touching the walls of the beaker. Usingthe lever on the left side of the apparatus, the platform supporting thebeaker is carefully raised until the surface of water or n-hexadecane is2-3 mm from the lower edge of the film strip. The door to the apparatusis closed, the “Configure” option is chosen from the “Initialize” menuof the computer, the “Automatic” option is chosen from the “Experiment”menu, and the computer program then calculates the time for a scan. Theapparatus then raises and lowers the liquid so that the scan is taken(the advancing angle is measured as the liquid moves up and over thesurface, while the receding angle is determined as the liquid moves downand away from the surface of the plastic film). The “Least Squares”option is then selected from the “Analysis” menu, and the averagereceding contact angle is calculated from the scan of the film sample.Three separate films are prepared for each material to be tested aspreviously described. The 95% confidence interval for the average of the3 scans is typically about 1.2°. This procedure is repeated for waterand n-hexadecane.

Examples 1-4 and Comparative Examples C1-C3

[0208] This series of experiments was run to show the overallimprovement in advancing contact angles (ACA) and receding contactangles (RCA) against water and n-hexadecane demonstrated by subericacid-derived polyester polymers when both pendant and terminalC₄F₉-groups were present, as compared when only pendant C₄F₉-groups oronly terminal C₄F₉-groups were present.

[0209] In Comparative Example C1, contact angles were measured for 1/1FBSEE/SBA, which contained pendant C₄F₉-groups only.

[0210] In Comparative Examples C2 and C3, contact angles were measuredfor 2/1 MeFBSE/SBA, which contained terminal C₄F₉-groups only. InComparative Example C2, the polyester reaction was catalyzed using pTSA(I), whereas in Comparative Example C3, the polyester reaction wascatalyzed using CF₃SO₃H (II).

[0211] In Examples 1-4, FBSEE diol, contact angles were measured forMeFBSE alcohol and SBA diacid reacted at molar ratios to give twoterminal C₄F₉-groups and 1, 2, 2 and 3 pendant C₄F₉-groups, respectively(the number of pendant groups is equal to the theoretical number ofFBSEE diol units in the polyester). For Example 2, the polyesterreaction product was not washed (I), while for Example 3, the polyesterwas twice washed with water (II).

[0212] Results from the contact angle measurements are shown in TABLE 1.TABLE 1 Water: n-hexadecane: Ex. Polyester Composition ACA, ° RCA, °ACA, ° RCA, ° C1   1/1 FBSEE/SBA 112 95 75 69 C2   2/1 MeFBSE/SBA (I)114 87 79 69 C3   2/1 MeFBSE/SBA (II) 103 77 64 29 1 1/2/2FBSEE/MeFBSE/SBA 119 98 79 67 2 2/2/3 FBSEE/MeFBSE/SBA 112 89 81 56 (I)3 2/2/3 FBSEE/MeFBSE/SBA 122 107 79 74 (II) 4 3/2/4 FBSEE/MeFBSE/SBA 120100 79 74

[0213] The data in TABLE 1 show that polyesters containing both pendantand terminal C₄F₉-groups demonstrated overall higher contact angles whencompared to the polyesters containing only pendant or only terminalC₄F₉-groups. Comparing Examples 2 and 3, contact angle results improvedwhen the product was water-washed.

[0214] TABLE 1—Polyester Preparations

[0215] 1/1 FBSEE/SBA—In a reaction flask equipped with stirrer, heaterand condenser with water trap were reacted 1.885 g (5 mmol) of FBSEE and0.871 g (5 mmol) of SBA in the presence of two drops of CF₃SO₃H in 100 gof toluene. The resulting mixture was heated to reflux for 2 hours, andthe formed water was removed until, from FTIR analysis, no more hydroxylsignal was observed. Then, 1 g of NaHCO₃ was added, and the mixture wasstirred for another 10 minutes. The solid was removed by filtration andthe obtained solution was rotary evaporated to strip off all thesolvent. he residue solid was dissolved in EtOAc.

[0216] 2/1 MeFBSE/SBA (I)—In a reaction flask equipped with stirrer,heater and condenser with water trap were reacted 3.57 g (10 mmol) ofMeFBSE and 0.87 g (5 mmol) of SBA in 50 g of toluene containing 0.2 g ofpTSA catalyst. The mixture was refluxed for 10 hours while removing theformed water. After removing the solids by filtration and removing thetoluene using rotary evaporation, the residue solid was dissolved inEtOAc.

[0217] 2/1 MeFBSE/SBA (II)—In a reaction flask equipped with stirrer,heater and condenser with water trap were reacted 3.57 g (10 mmol) ofMeFBSE and 0.87 g (5 mmol) SBA in 100 g of toluene containing 2 drops ofCF₃SO₃H catalyst. The resulting mixture was refluxed for 2 hours whileremoving the formed water. After removing the solids by filtration andremoving the toluene using rotary evaporation, the residue solid wasdissolved in EtOAc.

[0218] 1/2/2 FBSEE/MeFBSE/SBA—In a reaction flask equipped with stirrer,heater and condenser with water trap were first reacted 7.54 g (20 mmol)FBSEE and 6.968 g (40 mmol) of SBA in 150 g of toluene containing 2drops of CF₃SO₃H catalyst. The resulting mixture was refluxed for 2hours while removing the formed water. Then, 14.30 g (40 mmol) of MeFBSEwas added, and the mixture was refluxed for an additional 5 hours afterwhich, from FTIR analysis, no more hydroxyl signal was observed. Aftercooling mixture down to room temperature, the resulting reaction productwas washed with two 20 mL aliquots of deionized water, with the desiredproduct remaining in the top organic layer. After using rotaryevaporation to strip off all the toluene, the residue solid wasdissolved in EtOAc.

[0219] 2/2/3 FBSEE/MeFBSE/SBA—In a reaction flask equipped with stirrer,heater and condenser with water trap were reacted 1.758 g (5 mmol) ofMeFBSE, 1.885 g (5 mmol) FBSEE and 1.305 g (7.5 mmol) of SBA in 100 g oftoluene containing two drops of CF₃SO₃H. The resulting mixture washeated to reflux for four hours while removing the formed water. Afterreaction, a sample of the mixture was removed and isolated (I). Theremaining mixture portion was washed with two 20 mL aliquots ofdeionized water. The isolated top organic solution containing purifiedproduct was then isolated (II).

[0220] 3/2/4 FBSEE/MeFBSE/SBA—In a reaction flask equipped with stirrer,heater and condenser with water trap were reacted 2.262 g (6 mmol) ofFBSEE, 1.428 g (4 mmol) of MeFBSE and 1.392 g (8 mmol) of SBA in 80 g oftoluene containing 2 drops of CF₃SO₃H catalyst. The resulting mixturewas refluxed for 2 hours while removing the formed water by Dean-Startrap until, from FTIR analysis, no more hydroxyl signal was observed. Tothe mixture was then added 0.75 g of CaO, and the neutralized mixturewas stirred at 45° C. for 0.5 hour. The mixture was filtered to removedthe solid and solvent was stripped from the resulting filtrate usingrotary evaporation. The resulting solid was dissolved in THF.

Examples 5-13 and Comparative Examples C4-C7

[0221] This series of experiments was run to show the overallimprovement in advancing contact angles (ACA) and receding contactangles (RCA) against water and n-hexadecane demonstrated by adipicacid-derived polyester polymers when both pendant and terminalC₄F₉-groups were present, as compared when only pendant C₄F₉-groups oronly terminal C₄F₉-groups were present.

[0222] In Comparative Examples C4-C5, contact angles were measured for1/1 FBSEE/ADA polyesters (using pTSA and CF₃SO₃H catalyst,respectively), which contained pendant C₄F₉-groups only.

[0223] In Comparative Example C6, contact angles were measured for 2/1MeFBSE/ADA, which contained terminal C₄F₉-groups only.

[0224] In Comparative Example C7, contact angles were measured for 1/2/2HDO/MeFBSE/ADA, which contained terminal C₄F₉-groups only as it wasderived from a non-R_(f) group containing diol, hexanediol.

[0225] In Example 5 and 6, contact angles were measured for 1/2/2FBSEE/MeFBSE/ADA, made with bicarbonate treatment and with a water wash,respectively. This polymer theoretically contained one pendantC₄F₉-group and two terminal C₄F₉-groups.

[0226] In Example 5 and 6, contact angles were measured for 1/2/2FBSEE/MeFBSE/ADA, made with bicarbonate treatment (I) and with a waterwash (II), respectively. These polymers theoretically contained onependant C₄F₉-group and two terminal C₄F₉-groups.

[0227] In Examples 7-11, contact angles were measured for 2/2/3FBSEE/MeFBSE/ADA made using various catalysts, reaction times andderived from both adipic acid and adipoyl chloride. These polymerstheoretically contained two pendant C₄F₉-groups and two terminalC₄F₉-groups.

[0228] In Examples 12 and 13, contact angles were measured for 3/2/4FBSEE/MeFBSE/ADA made by reacting all ingredients at once (Ex. 12) andby first reacting the FBSEE diol with the ADA diacid, followed byreaction with the MeFBSE alcohol (Ex. 13). These polymers theoreticallycontained three pendant C₄F₉-groups and two terminal C₄F₉-groups.

[0229] Results from the contact angle measurements are shown in TABLE 2.TABLE 2 Water: n-hexadecane: Ex. Polyester Composition ACA, ° RCA, °ACA, ° RCA, ° C4    FBSEE/ADA (I) 98 70 78 66 C5    FBSEE/ADA (II) 10775 74 71 C6   2/1 MeFBSE/ADA 107 68 63 33 C7 1/2/2 HDO/MeFBSE/ADA 104 8579 70  5 1/2/2 FBSEE/MeFBSEE/ADA 119 99 79 70 (I)  6 1/2/2FBSEE/MeFBSEE/ADA 120 95 80 70 (II)  7 2/2/3/ FBSEE/MeFBSE/ADA 95 76 7968 (I)  8 2/2/3/ FBSEE/MeFBSE/ADA 104 75 64 27 (II)  9 2/2/3/FBSEE/MeFBSE/ADA 120 103 80 74 (III) 10 2/2/3/ FBSEE/MeFBSE/ADA 107 9279 69 (IV) 11 2/2/3/ FBSEE/MeFBSE/ADC 113 91 73 55 12 3/2/4FBSEE/MeFBSE/ADA 118 95 79 74 (I) 13 3/2/4 FBSEE/MeFBSE/ADA 95 75 81 70(II)

[0230] The data in TABLE 2 show that, on the average, both advancing andreceding contact angles against water and n-hexadecane are greater forthe polyesters containing both pendant and terminal —C₄F₉ groups, ascompared to the polyesters containing only pendant or only terminalgroups. The average values for Examples 5-13 vs. Comparative ExamplesC4-C7 are as follows: water ACA: 110° vs. 104°; water RCA: 89° vs. 75°;n-hexadecane ACA: 77° vs. 74°; n-hexadecane RCA: 64° vs. 60°.

[0231] Table2—Polyester Preparations

[0232] 1/1 FBSEE/ADA (I)—In a reaction flask equipped with stirrer,heater and condeser with water trap were reacted 3.77 g (10 mmol) ofFBSEE and 1.46 g (10 mmol) of ADA in the presence of 0.01 g of pTSA in100 g of toluene. After refluxing for 5 hours and continually removingthe formed water, FTIR analysis showed almost no remaining hydroxylgroups. The toluene was removed by rotary evaporation and the residuesolid was dissolved in acetone.

[0233] 1/1 FBSEE/ADA (II)—In a reaction flask equipped with stirrer,heater and condenser with water trap were reacted 1.885 g (5 mmol) ofFBSEE and 0.73 g of ADA in the presence of two drops of CF₃SO₃H in 100 gof toluene. The mixture was heated to reflux for 2 hours, and the formedwater was continually removed until no more hydroxyl signal was observedusing FTIR analysis. Then, 0.5 g of NaHCO₃ was added, and the resultingmixture was stirred for 10 minutes, during which time the light yellowcolor disappeared. The mixture was filtered to remove all solid, thesolvent was removed by rotary evaporation, and the residue solid wasdissolved in EtOAc.

[0234] 2/1 MeFBSE/ADA—In a reaction flask equipped with stirrer, heaterand condenser with water trap were reacted 7.14 g (20 mmol) of MeFBSEand 1.46 g (10 mmol) of ADA in 200 g of toluene containing 2 drops ofCF₃SO₃H catalyst. The resulting mixture was refluxed for 2 hours whileremoving the formed water. The reaction mixture was treated with excessNaHCO₃. After removing the solids by filtration and removing the tolueneusing rotary evaporation, the residue polyester solid was dissolved inEtOAc.

[0235] 1/2/2 HDO/MeFBSE/ADA—In a reaction flask equipped with stirrer,heater and condenser with water trap were reacted 1.190 g (10 mmol) ofHDO and 2.927 g (20 mmol) of ADA in 100 g of toluene containing 2 dropsof CF₃SO₃H catalyst. The resulting mixture was refluxed for 2 hourswhile removing the formed water. Then 7.152 g (20 mmol) of MeFBSE wasadded, and the new resulting mixture was refluxed for an additional twohours. The reaction mixture was treated with NaHCO₃ at 60° C. for 0.5hour. After removing the solids by filtration and removing the tolueneusing rotary evaporation, the residue solid was dissolved in EtOAc.

[0236] 1/2/2 FBSEE/MeFBSE/ADA (I,II)—In a reaction flask equipped withstirrer, heater and condenser with water trap were first reacted 3.809 g(10.1 mmol) FBSEE and 2.923 g (20.1 mmol) of ADA in 100 g of toluenecontaining 2 drops of CF₃SO₃H catalyst. The resulting mixture wasrefluxed for 1 hour while removing the formed water. Then 7.152 g (20mmol) of MeFBSE was added, and the new resulting mixture was refluxedfor another 4 hours, after which no hydroxyl signal was observed usingFTIR analysis. The solution was then separated into two portions, (I)and (II). 1.0 g of NaHCO₃ was added to portion (I), and the resultingmixture was stirred for 0.5 hour. Rotary evaporation was used to stripoff the toluene, and the residue solid from portion (I) was dissolved inEtOAc. Then portion (II) was washed twice with deionized water, theseparated top organic layer containing product was stripped, then theresulting residue solid was dissolved in THF.

[0237] 2/2/3 FBSEE/MeFBSE/ADA (I)—In a reaction flask equipped withstirrer, heater and condenser with water trap were reacted 1.885 g (5mmol) of FBSEE, 1.785 g (5 mmol) of MeFBSE and 1.095 g (7.5 mmol) of ADAin 100 g of toluene containing 0.057 g of pTSA catalyst. The resultingmixture was refluxed for 10 hours while continually removing the formedwater. FTIR analysis of the reaction mixture indicated a small amount ofunreacted hydroxyl. Toluene was removed using rotary evaporation, andthe residue solid was dissolved in acetone.

[0238] 2/2/3 FBSEE/MeFBSE/ADA (II)—In a reaction flask equipped withstirrer, heater and condenser with water trap were reacted 3.73 g (10mmol) of FBSEE, 3.57 g (10 mmol) of MeFBSE and 2.19 g (15 mmol) of ADAin 100 g of toluene containing 0.02 g of pTSA catalyst. The resultingmixture was refluxed for 5 hours while removing the formed water, afterwhich no hydroxyl signal was detected using FTIR analysis. The toluenewas then removed using rotary evaporation, and the residue solid wasdissolved in THF.

[0239] 2/2/3 FBSEE/MeFBSE/ADA (III)—In a reaction flask equipped withstirrer, heater and condenser with water trap were reacted 1.885 g (5mmol) of FBSEE, 1.785 g (5 mmol) of MeFBSE and 1.095 g (7.5 mmol) of ADAin 120 g of toluene containing 2 drops of CF₃SO₃H catalyst. Theresulting mixture was refluxed for 4 hours while removing the formedwater. The solution was then treated with NaHCO₃. After removing thesolids by filtration and removing the toluene using rotary evaporation,the residue solid was dissolved in EtOAc.

[0240] 2/2/3 FBSEE/MeFBSE/ADA (IV)—In a reaction flask equipped withstirrer, heater and condenser with water trap were reacted 11.435 g(30.33 mmol) of FBSEE, 10.736 g (30.07 mmol) of MeFBSE and 6.581 g(45.07 mmol) of ADA in 200 g of toluene containing 2 drops of CF₃SO₃Hcatalyst. The reaction mixture was refluxed for 2 hours whilecontinually removing the formed water, then was treated with NaHCO₃.After removing the solids by filtration and removing the toluene usingrotary evaporation, the residue solid was dissolved in acetone.

[0241] 2/2/3 FBSEE/MeFBSE/ADC—To a 100 mL flask equipped with stirrer,heater, distillation column and addition funnel were charged 1.555 g(10.7 mmol) of ADC and 50 g of toluene. Then from an additional funnelwas added a solution of 2.677 g (7.1 mmol) FBSEE and 2.535 g (7.1 mmol)MeFBSE in 5 g of CH₂Cl₂ and 5 g EtOAc at room temperature over a ½ hourperiod. After addition, the solution was refluxed for 10 hours, afterwhich, from FTIR analysis, no more hydroxyl signal was observed. Rotaryevaporation was used to strip off the solvent, and the residue solid wasdissolved in THF.

[0242] 3/2/4 FBSEE/MeFBSE/ADA (I)—In a reaction flask equipped withstirrer, heater and condenser with water trap were reacted 2.262 g (6mmol) of FBSEE, 1.428 g (4 mmol) of MeFBSE and 1.168 g (8 mmol) ofadipic acid (AA) in 100 g of toluene containing two drops of CF₃SO₃Hcatalyst. The resulting mixture was refluxed for 2 hours whilecontinually removing the formed water. The reaction mixture was thentreated with CaO at 60° C. for 0.5 hour. After removing the solids byfiltration and removing the toluene using rotary evaporation, theresidue solid was dissolved in EtOAc.

[0243] 3/2/4 FBSEE/MeFBSE/ADA (II)—In a reaction flask equipped withstirrer, heater and condenser with water trap were first reacted 1.885 g(5 mmol) FBSEE and 1.468 g (10.05 mmol) of ADA in 120 g of toluenecontaining 2 drops of CF₃SO₃H catalyst. The resulting mixture wasrefluxed for 1 hour while continually removing the formed water. Then3.782 g (10 mmol) of additional FBSEE was added and the resultingmixture refluxed for an additional hour. Then 1.465 g (10 mmol) of ADAwas added, and the new mixture was refluxed for one hour. Finally, 3.58g (10 mmol) of MeFBSE was added, and the final mixture was refluxed for5 hours. The reaction mixture was treated with NaHCO₃. After removingthe solids by filtration and removing the toluene using rotaryevaporation, the residue solid was dissolved in EtOAc.

Examples 14 and Comparative Examples C8-C10

[0244] This series of experiments was run to show advancing contactangles (ACA) and receding contact angles (RCA) against water andn-hexadecane demonstrated by polyester polymer containing pendantC₄F₉-groups and terminal C₈F₁₇-groups as compared to polyester polymerscontaining pendant C₄F₉—, C₆F₁₃- and/or C₈F₁₇-groups but no terminalR_(f) groups.

[0245] In Comparative Examples C8, contact angles were measured for 1/1FHSEE/ADA polyester, which contained pendant C₆F₁₃-groups only.

[0246] In Comparative Examples C9, contact angles were measured for0.2/0.8/1.0 FHSEE/FBSEE/ADA polyester, which theoretically contained 20%pendant C₆F₁₃-groups and 80% pendant C₄F₉-groups.

[0247] In Comparative Example C10, contact angles were measured for 1/1FOSEE/ADA, which contained pendant C₈F₁₇-groups only.

[0248] In Example 14, contact angles were measured for 2/2/3FBSEE/MeFOSE/ADA, which theoretically contained two pendant C₄F₉-groupsand two terminal C₈F₁₇-groups.

[0249] Results from the contact angle measurements are shown in TABLE 3.TABLE 3 n- Water: hexadecane: Ex. Polyester Composition ACA RCA ACA RCAC8 1/1 FHSEE/ADA 116 81 74 57 C9 0.2/0.8/1 FHSEE/FBSEE/ADA 123 81 72 48C10 1/1 FOSEE/ADA 111 78 76 59 14 2/2/3/ FBSEE/MeFOSE/ADA 118 102 82 77

[0250] The data in TABLE 3 show that the polyester of Example 14,containing pendant C₄F₉-groups and terminal C₈F₁₇-groups, exhibitssuperior contact angles to all of the comparative polyesters containingonly pendant R_(f)-groups. Especially notable is the advantage inperformance over the polyester of Comparative Example C10, whichcontains only the longer-chain C₈F₁₇-groups that one skilled in the artwould expect to exhibit greater repellency.

[0251] Table 3—Polyester Preparations

[0252] 1/1 FHSEE/ADA—In a reaction flask equipped with stirrer, heaterand condenser with water trap were reacted 4.73 g (10 mmol) of FHSEE and1.46 g (10 mmol) of ADA in the presence of two drops of CF₃SO₃H in 100 gof toluene. The resulting mixture was heated to reflux for 5 hours whileremoving the formed water until no further hydroxyl signal was evidentusing FTIR analysis. The toluene was removed by rotary evaporation, andthe residue solid was dissolved in THF.

[0253] 0.2/0.8/1 FHSEE/FBSEE/ADA—In a reaction flask equipped withstirrer, heater and condenser with water trap were reacted 0.95 g (2mmol) of FHSEE, 2.98 g (8 mmol) of MeFBSEE and 1.46 g (10 mmol) of ADAin the presence of 0.02 g of pTSA in 100 g of toluene. The mixture washeated to reflux for 5 hours while continually removing the formedwater. The toluene was removed by rotary evaporation, and the residuesolid was dissolved in EtOAc.

[0254] 1/1 FOSEE/ADA—In a reaction flask equipped with stirrer, heaterand condenser with water trap were reacted 5.876 g (10.55 mmol) of FOSEEand 1.47 g (10.6 mmol) of ADA in the presence of two drops of CF₃SO₃H in100 g of toluene. The resulting mixture was refluxed for 2 hours, andthe formed water was removed until, from FTIR analysis, no more hydroxylsignal was observed. Then, 1 g of NaHCO₃ was added and the mixture wasstirred for another 10 minutes. The solution was filtered to remove thesolid and the obtained solution was rotary evaporated to strip off allthe solvent. The residue solid was dissolved in EtOAc.

[0255] 2/2/3 FBSEE/MeFOSE/ADA—In a reaction flask equipped with stirrer,heater and condenser with water trap were reacted 2.523 g (6.69 mmol) ofFBSEE, 3.727 g (6.69 mmol) of MeFOSE and 1.473 g (10.09 mmol) of ADA in150 g of toluene containing 2 drops of CF₃SO₃H catalyst. The mixture wasrefluxed for 2 hours while continually removing the formed water. Thereaction mixture was treated with NaHCO₃ at 70° C. for 0.5 hour. Afterremoving the solids by filtration and removing the toluene using rotaryevaporation, the residue solid was dissolved in EtOAc.

Examples 15, 16 and 9

[0256] This series of experiments was run to show advancing contactangles (ACA) and receding contact angles (RCA) against water andn-hexadecane demonstrated by polyester polymers containing two pendantand terminal C₄F₉-groups and derived from three different diacids:dodecanedioic acid (DDA, HOOC(CH₂)₁₀COOH, Example 15), azelaic acid(AZA, HOOC(CH₂)₇COOH, Example 16) and adipic acid (ADA, HOOC(CH₂)₂COOH,Example 9, taken from TABLE 2). All three polyesters were made inapproximately the same scale using the same acid catalyst, CF₃SO₃H.

[0257] Results are presented in TABLE 4. TABLE 4 Water: n-hexadecane:Ex. Polyester Composition ACA, ° RCA, ° ACA, ° RCA, ° 15 2/2/3FBSEE/MeFBSE/DDA 110 83 80 71 16 2/2/3 FBSEE/MeFBSE/AZA 104 73 70 51  92/2/3 FBSEE/MeFBSE/ADA 120 103 80 74 (I)

[0258] The data in TABLE 4 show that all of the diacids impart highadvancing and receding contact angles to the polyesters.

[0259] Table 4—Polyester Preparations

[0260] 2/2/3 FBSEE/MeFBSE/DDA—In a reaction flask equipped with stirrer,heater and condenser with water trap were reacted 1.888 g (5 mmol) ofFBSEE, 1.799 g (5 mmol) of MeFBSE and 1.730 g (7.5 mmol) of DDA in 100 gof toluene containing 2 drops of CF₃SO₃H catalyst. The resulting mixturewas refluxed for 2 hours while removing the formed water. Then thereaction mixture was treated with NaHCO₃ at 50° C. for 0.5 hour. Afterremoving the solids by filtration and removing the toluene using rotaryevaporation, the residue solid was dissolved in EtOAc.

[0261] 2/2/3 FBSEE/MeFBSE/AZA—In a reaction flask equipped with stirrer,heater and condenser with water trap were reacted 1.890 g (5 mmol) ofFBSEE, 1.788 g (5 mmol) of MeFBSE and 1.425 g (7.5 mmol) of AZA in 100 gof toluene containing 2 drops of CF₃SO₃H catalyst. The mixture wasrefluxed for 2 hours while removing the formed water. The reactionmixture was treated with NaHCO₃ at 50° C. for 0.5 hour. After removingthe solids by filtration and removing the toluene using rotaryevaporation, the residue solid was dissolved in EtOAc.

[0262] 2/2/3 FBSEE/MeFBSE/ADA (III)—In a reaction flask equipped withstirrer, heater and condenser with water trap were reacted 1.885 g (5mmol) of FBSEE, 1.785 g (5 mmol) of MeFBSE and 1.095 g (7.5 mmol) of ADAin 120 g of toluene containing 2 drops of CF₃SO₃H catalyst. Theresulting mixture was refluxed for 4 hours while removing the formedwater. The solution was then treated with NaHCO₃. After removing thesolids by filtration and removing the toluene using rotary evaporation,the residue solid was dissolved in EtOAc.

Example 17

[0263] This experiment was run to show advancing contact angles (ACA)and receding contact angles (RCA) against water and n-hexadecanedemonstrated by a polyester polymer (MeFBSE/ADA/FBSEE-Acr) made bypolymerizing an acrylate monomer containing one pendant C₄F₉-group, oneterminal C₄F₉-group and one polymerizable group.

[0264] Results are presented in TABLE 5. TABLE 5 Water: n-hexadecane:Ex. Polyester Composition ACA, ° RCA, ° ACA, ° RCA, ° 17MeFBSE/ADA/FBSEE-Acr 117 99 79 70

[0265] The data in TABLE 5 show that the polyester acrylate polymerhaving pendant and terminal C₄F₉-groups demonstrates excellent advancingand receding contact angles.

[0266] Table 5—Polyester Preparations

[0267] 1/1/1 MeFBSE/ADA/FBSEE-Acr—In a reaction flask equipped withstirrer, heater and condenser with water trap were reacted 3.57 g (10mmol) of MeFBSE, 3.77 g (10 mmol) of FBSEE, 1.46 g (10 mmol) of ADA and0.72 g (10 mmol) of AA in 100 g of toluene containing 2 drops of CF₃SO₃Hcatalyst. The resulting mixture was refluxed for 4 hours while removingthe formed water. Then, 0.005 g of VAZO™ 64 initiator was added, and theactivated mixture was reacted at 65° C. for 10 hours. The reactionmixture was treated with excess CaO at 70° C. for 0.5 hours. Afterremoving the solids by filtration and removing the toluene using rotaryevaporation, the residue solid was dissolved in EtOAc.

Examples 18-22 and Comparative Examples C11-C12

[0268] This series of experiments was run to illustrate that thepolyesters of this invention are effective in imparting repellency tolimestone, a hard porous substrate.

[0269] For Comparative Example C11, no polyurethane was evaluated (i.e.,an untreated tile was evaluated for stain resistance).

[0270] For Comparative Example C12, FC-759 (available from 3M Company,St. Paul, Minn.), which contains a fluoropolymer having pendantC₈F₁₇-groups but having no terminal R_(f)-groups, was evaluated.

[0271] For Examples 18-22, various polyesters of this invention,containing both pendant and terminal C₄F₉-groups, were evaluated. Thepolyesters were the same as evaluated earlier for advancing and recedingcontact angles in Examples 6, 3, 4, 10 and 15, respectively.

[0272] Using the earlier-described Staining Test, the staining agentsemployed were: anti-freeze coolant (AFC), grape juice (GJ), soy sauce(SS), used 10W30 motor oil (MO), Paul Masson™ Burgundy wine (WIN), watersaturated with Taster's Choice coffee (COF), STP™ heavy duty brake fluid(BF) and Mazola™ corn oil (CO). For this test, a 5-point rating scalewas used, with a rating of “0” indicates essentially no stain remainingand a rating of “5” indicating very poor stain resistance. A total isalso presented, with a lower total indicating better overall stainresistance.

[0273] Results from these evaluations are presented in TABLE 6. TABLE 6Stain Resistance Rating To: Ex. Polyurethane Composition Total AFC GJ SSMO WIN COF BF CO C11 No treatment 40 5 5 5 5 5 5 5 5 C12 FC-759 12 1 4 10 4 2 0 0 18 1/2/2 FBSEE/MeFBSEE/ADA (II) 12 0 2 1 1 2 2 2 2 19 2/2/3FBSEE/MeFBSE/SBA (II) 15 0 1 2 2 2 1 4 3 20 3/2/4 FBSEE/MeFBSE/SBA 19 13 3 2 3 1 3 3 21 2/2/3/FBSEE/MeFBSE/ADA (IV) 10 0 3 1 1 2 1 2 0 22 2/2/3FBSEE/MeFBSE/DDA 7 0 2 0 1 2 1 1 0

[0274] The data in TABLE 6 show that the polyesters containing terminaland pendant C₄F₉-groups imparted comparable stain resistance to theFC-759 treatment, which contained pendant C₈F₁₇-groups. This issurprising as one skilled in the art would expect a treatment containinglonger chain C₈F₁₇-groups to outperform a treatment containing shorterchain C₄F₉-groups.

Examples 23-29

[0275] In Examples 23-29, a variety of polyesters of this invention weresynthesized and evaluated for advancing and receding contact angles vs.water and n-hexadecane.

[0276] Hydrophilic polyesters, having water-solubilizing groups (e.g.,the polyoxyethylene diol-derived polyester of Example 23, the citricacid-derived polyester of Example 24, or the polyoxyethylenedicarboxylic acid-derived polyester of Example 25) are presented.

[0277] Conversely, very hydrophobic polyesters having long-chainhydrocarbon groups (e.g., the dimer acid-derived polyesters of Examples26-29) are presented.

[0278] Results from the contact angle measurements are shown in TABLE 7.

[0279] Polyester Preparations

[0280] 2/1.85/0.15/3 MeFBSE/FBSEE/75-H-1400/ADA—In a 100 mL three-neckflask equipped with stirrer, heater and condenser with Dean-Stark trapwere reacted 17.43 g (46.2 mmol) of FBSEE, 9.31 g (3.8 mmol) of75-H-1400, 17.65 g (49.4 mmol) of MeFBSE and 11.02 g (75.5 mmol) ADA in250 g of toluene with 4 drops of CF₃SO₃H. The resulting mixture washeated to reflux under nitrogen for four hours while removing the formedwater in the Dean-Stark trap. The catalyst was removed by addition ofCaO (1 g) followed by filtration. The toluene was removed by rotaryevaporation, and the residue solid was dissolved at 25% solids in THF.

[0281] 4/1/2 MeFBSE/FBSEE/CA—In a 100 mL three-neck flask equipped withstirrer, heater and condenser with Dean-Stark trap were reacted 3.77 g(10 mmol) of FBSEE, 14.28 g (40 mmol) of MeFBSE and 4.20 g (20 mmol) ofcitric acid in 200 g of toluene with 4 drops of CF₃SO₃H. The mixture washeated to reflux under nitrogen for 6 hours while removing the waterformed in the Dean-Star trap. The catalyst was removed by addition ofCaO (1 g) followed by filtration. The toluene was removed by rotaryevaporation, and the obtained residue solid was dissolved at 25% solidsin EtOAc.

[0282] 2/2/2.710.3 MeFBSE/FBSEE/ADA/PEG Diacid—In a 100 mL three-neckflask equipped with stirrer, heater and condenser with Dean-Stark trapwere reacted 19.61 g (52 mmol) of FBSEE, 18.596 g (52.1 mmol) of MeFBSE,10.245 g (70.2 mmol) of ADA and 4.734 g (7.9 mmol) of PEG diacid in 350g of toluene with 4 drops of CF₃SO₃H. The mixture was heated to refluxunder nitrogen for 10 hours while removing the formed water in theDean-Star trap. The catalyst was removed by addition of CaO (1 g)followed by filtration. The toluene was removed by rotary evaporation,and the obtained residue solid was dissolved at 25% solids in EtOAc.

[0283] 2/2/2.810.2 MeFBSE/FBSEE/DDA/Dimer Acid—In a 100 mL three-neckflask equipped with stirrer, heater and condenser with Dean-Stark trapwere reacted 15.2 g (40.3 mmol) of FBSEE, 14.5 g (40.6 mmol) of MeFBSE,12.9 g (56 mmol) of DDA (HOOC(CH₂)₁₀COOH) and 2.3 g (4 mmol) of dimeracid in 300 g of toluene with 4 drops of CF₃SO₃H. The mixture was heatedto reflux under nitrogen for 10 hours while removing the water formed inthe Dean-Star trap. The catalyst was removed by addition of CaO (1 g)followed by filtration. The toluene was removed by rotary evaporation,and the obtained residue solid was dissolved at 25% solids in EtOAc.

[0284] 21212.7/0.3 MeFBSE/FBSEE/ADA/Dimer Acid—In a 100 mL three-neckflask equipped with stirrer, heater and condenser with Dean-Stark trapwere reacted 15.08 g (40 mmol) of FBSEE, 14.28 g (40 mmol) of MeFBSE,7.884 g (54 mmol) of ADA and 3.42 g (6 mmol) of dimer acid in 300 g oftoluene with 4 drops of CF₃SO₃H. The mixture was heated to reflux undernitrogen for 10 hours while removing the water formed in the Dean-Startrap. After removing catalyst by addition of CaO (1 g) followed byfiltration, a solid residue was obtained after removing the toluene byrotary evaporation. The solid was dissolved at 25% solids in EtOAc.

[0285] 2/2/2/1 MeFBSE/FBSEE/ADA/Dimer Acid—In a 100 mL three-neck flaskequipped with stirrer, heater and condenser with Dean-Stark trap werereacted 15.2 g (40.3 mmol) of FBSEE, 14.2 g (39.8 mmol) of MeFBSE, 5.8 g(39.7 mmol) of ADA and 12.2 g (21.4 mmol) of dimer acid in 300 g oftoluene with 4 drops of CF₃SO₃H. The mixture was heated to reflux undernitrogen for 10 hours while removing the water formed in the Dean-Startrap. After removing catalyst by addition of CaO (1 g) followed byfiltration, a solid residue was obtained after removing the toluene byrotary evaporation. The solid was dissolved at 25% solids in EtOAc.

[0286] 2/1/1/1 MeFBSE/FBSEE/ADA/Dimer Acid—In a 100 mL three-neck flaskequipped with stirrer, heater and condenser with Dean-Stark trap werereacted 7.6 g (20.2 mmol) of FBSEE, 14.4 g (40.3 mmol) of MeFBSE, 2.92 g(20 mmol) of ADA and 12.5 g (20.24 mmol) of dimer acid in 300 g oftoluene with 4 drops of CF₃SO₃H. The mixture was heated to reflux undernitrogen for 10 hours while removing the water formed in the Dean-Startrap. After removing catalyst by addition of CaO (1 g) followed byfiltration, a solid residue was obtained after removing the toluene byrotary evaporation. The solid was dissolved at 25% solids in EtOAc.

We claim:
 1. A fluorochemical ester composition comprising: one or moreoligomers wherein each oligomer comprises (i) at least onefluorine-containing repeatable unit and (ii) at least onefluorine-containing terminal group, and wherein said compounds oroligomers comprise the condensation reaction product of: (a) one or morefluorinated polyols; (b) one or more polyacyl compounds; and (c) one ormore monofunctional fluorine-containing compounds comprising afunctional group that is reactive with the hydroxyl group of said polyol(a) or with the acyl group of the polyacyl compounds (b).
 2. Theoligomers of claim 1 further comprising the reaction product of one ormore water-solubilizing compounds comprising one or more watersolubilizing groups and at least one electrophilic or nucleophilicmoiety, said solubilizing groups independently pendant from therepeating unit, or terminal portion.
 3. The water solubilizing oligomersof claim 2 wherein said water-solubilizing group is selected from thegroup consisting of carboxylate, sulfate, phosphate, sulfonate,phosphonate, ammonium, and quaternary ammonium groups.
 4. The oligomersof claim 1 further comprising the reaction product of one or morepolymerizable compounds comprising one or more polymerizable groups andat least one electrophilic or nucleophilic moiety, said polymerizablegroups independently pendant from the repeating unit, or terminalportion.
 5. The polymerizable oligomers of claim 4, wherein saidpolymerizable groups are selected from the group consisting of acrylate,methacrylate, vinyl allyl, and glycidyl groups.
 6. The oligomers ofclaim 1 of the formulaR_(f)Q[OR²]_(o)[—OC(O)—R¹—C(O)O—R²O—]_(n)[C(O)—R¹—C(O)]_(m)—Z  (I)wherein: o is a number from 0 to 1 inclusive; n is a number from 1 to 10inclusive; m is is number from 0 to 1 inclusive; R_(f) is aperfluoroalkyl group having 1 to 12 carbon atoms, or aperfluoroheteroalkyl group having 3 to about 50 carbon atoms with allperfluorocarbon chains present having 1 to 6, preferably 1 to 4 carbonatoms; Q is a divalent linking group; R¹ is a polyvalent organic groupsthat is a residue of a polyacyl compound, that is a straight or branchedchain alkylene, cycloalkylene, or heteroalkylene group of 1 to 14 carbonatoms; or an arylene of 6 to 12 carbon atoms; R² is a divalent organicgroup that is a residue of the polyol, at least a portion of which aresubstituted with or contain one or more perfluoroalkyl groups,perfluoroheteroalkyl groups, perfluoroheteroalkylene groups, or mixturesthereof; and Z is R_(f)Q—, a water-solubilizing group, or apolymerizable group.
 7. The oligomer of claim 6, wherein Q is selectedfrom the following structures, wherein each k is independently aninteger from 0 to about 20, R₁′ is hydrogen, phenyl, or alkyl of 1 toabout 4 carbon atoms, and R₂′ is alkyl of 1 to about 20 carbon atoms:—SO₂NR₁′(CH₂)_(k)O(O)C— —CONR₁′(CH₂)_(k)O(O)C— —(CH₂)_(k)O(O)C——CH₂CH(OR₂′)CH₂O(O)C— —(CH₂)_(k)C(O)O— —(CH₂)_(k)SC(O)——(CH₂)_(k)O(CH₂)_(k)O(O)C— —(CH₂)_(k)S(CH₂)_(k)O(O)C——(CH₂)_(k)SO₂(CH₂)_(k)O(O)C— —(CH₂)_(k)S(CH₂)_(k)OC(O)——(CH₂)_(k)SO₂NR₁′(CH₂)_(k)O(O)C— —(CH₂)_(k)SO₂— —SO₂NR₁′(CH₂)_(k)O——SO₂NR₁′(CH₂)_(k)— —(CH₂)_(k) _(O(CH) ₂)_(k)C(O)O——(CH₂)_(k)SO₂NR₁′(CH₂)_(k)C(O)O— —(CH₂)_(k) _(SO) ₂(CH₂)_(k)C(O)O——CONR₁′(CH₂)_(k)C(O)O— —(CH₂)_(k) _(S(CH) ₂)_(k)C(O)O——CH₂CH(OR₂′)CH₂C(O)O— —SO₂NR₁′(CH₂)_(k)C(O)O— —(CH₂)_(k)O——C_(k)H_(2k)—OC(O)NH— —C_(k)H_(2k)—NR₁′C(O)NH—, —OC(O)NR′(CH₂)_(k)——(CH₂)_(k)NR₁′— and —(CH₂)_(k)NR₁′C(O)O—


8. The oligomers of claim 1 of the formulaR_(f)Q[C(O)—R¹—C(O)O—R²O—]_(n)[C(O)—R¹—C(O)]_(m)—QR_(f) wherein: n is anumber from 1 to 10 inclusive; m is 1; R_(f) is a perfluoroalkyl grouphaving 1 to 12 carbon atoms, or a perfluoroheteroalkyl group having 3 toabout 50 carbon atoms with all perfluorocarbon chains present having 1to 6, preferably 1 to 4 carbon atoms; Q is a divalent linking group; R¹is a straight chain alkylene, of 1 to 14 carbon atoms; R² is apolyvalent organic group which is a residue of the polyol, that is astraight or branched chain alkylene, cycloalkylene, arylene orheteroalkylene group of 1 to 14 carbon atoms, or an arylene group of 6to 12 carbon atoms; at least a portion of R² groups comprise oneperfluoroalkyl group, perfluoroheteroalkyl group,perfluoroheteroalkylene group, or mixtures thereof.
 9. The compositionof claim 1 wherein the oligomer comprises the condensation reactionproduct of one or more fluorinated polyols, one or more non-fluorinatedpolyols, one or more polyacyl compound and one or more monofunctionalfluorine-containing compounds.
 10. The composition of claim 1 whereinthe oligomer comprises the condensation reaction product of one or morefluorinated polyols, an excess amount (relative to the polyol) of one ormore linear alkylene diacyl compounds, and sufficient fluorinatedmonoalcohols to react with the terminal acyl groups
 11. Thefluorochemical composition of claim 1 wherein the fluorine containinggroup of said polyol is a perfluoroalkyl group of 6 or fewer carbonatoms.
 12. The fluorochemical composition of claim 1 wherein thefluorine containing group of said polyol is a perfluoroalkyl group of 3to 5 carbon atoms.
 13. The fluorochemical composition of claim 1 whereinthe wherein the fluorine containing group of said polyol is aperfluoroalkyl group of is perfluorobutyl.
 14. The fluorochemicalcomposition of claim 1 wherein the monofunctional fluorine-containingcompound is a compound of the following formula I: R_(f)—Q′ wherein:R_(f) is selected from the group consisting of perfluoroalkyl grouphaving 1 to 12 carbon atoms, and perfluoroheteroalkyl group having 3 toabout 50 carbon atoms with all perfluorocarbon chains present having 6or fewer carbon atoms; Q′ is a functional group that is reactive withthe terminal acyl group of the polyacyl group or terminal hydroxy groupof the polyol.
 15. The monofunctional fluorine-containing compound ofclaim 14 wherein Q′ is selected from hydroxyl, secondary amino,oxazolinyl, oxazolonyl, acetyl, acetonyl, carboxyl, isocyanato, epoxy,aziridinyl, thio, ester and acyl halide groups.
 16. The fluorochemicalcomposition of claim 1 wherein said oligomers comprise the condensationreaction product of: (a) one or more fluorinated polyols; (b) one ormore polyacyl compounds; and (c) one or more monofunctionalfluorine-containing compounds comprising one functional group that isreactive with the hydroxyl group of said polyol (a) or with the acylgroup of the polyacyl compound (b).
 17. The fluorochemical compositionof claim 16 wherein said fluorochemical oligomer further comprises thereaction product of one or more non-fluorinated polyols.
 18. A coatingcomposition comprising a mixture comprising: (a) a solvent and (b) thefluorochemical composition of claim
 1. 19. The coating composition ofclaim 18 wherein said mixture comprises an aqueous solution, dispersionor suspension.
 20. The coating composition of claim 18 wherein thefluorochemical composition further comprises one or morewater-solubilizing groups.
 21. An article comprising a substrate havinga coating of the fluorochemical composition of claim 1 on one or moresurfaces of said substrate.
 22. The article of claim 21 wherein thefluorochemical composition further comprises one or morewater-solubilizing groups.
 23. The article of claim 21 wherein thefluorochemical composition further comprises one or polymerizablegroups.
 24. The article of claim 21 wherein the substrate is selectedfrom the group consisting of hard substrates and fibrous substrates. 25.A method of imparting repellency to a substrate comprising the steps of:applying the coating composition of claim 18 onto one or more surfacesof said substrate; and curing the coating composition at ambient orelevated temperature.
 26. A polymer composition comprising: (a) thefluorochemical composition of claim 1; and (b) at least onethermoplastic or thermoset polymer.
 27. The polymer composition of claim26 wherein said thermoplastic polymer is selected from the groupconsisting of polypropylene, polyethylene, polyacrylates,polymethacrylates, copolymers of ethylene and one or more alpha-olefins,polyesters, polyurethanes, polycarbonates, polyetherimides, polyimides,polyetherketones, polysulfones, polystyrenes, ABS copolymers,polyamides, fluoroplastics, and blends thereof; and said thermosetpolymer is selected from the group consisting of polyurethanes, epoxyresins, fluoroelastomers, polyacrylates, polymethacrylates, andunsaturated polyesters, and blends thereof.
 28. The polymer compositionof claim 26 wherein said composition is prepared by forming a melt blendof said fluorochemical composition and said thermoplastic polymer.
 29. Ashaped article comprising the polymer composition of claim 26, whereinsaid shaped article is selected from fibers, films, and molded articles.30. A process for preparing shaped article comprising the steps of (a)combining the fluorochemical composition of claim 1 and at least onethermoplastic polymer; and (b) melt processing the resultingcombination.